KR102146684B1 - Colored composition, film, color filter, pattern formation method, color filter manufacturing method, solid-state image sensor and infrared sensor - Google Patents

Abstract

It provides a colored composition capable of forming a film capable of transmitting infrared rays in a state where there is little noise derived from visible light. Further, a film using a colored composition, a color filter, a pattern forming method, a method for producing a color filter, a solid-state image sensor, and an infrared sensor are provided. The coloring composition contains a color material that blocks light in the visible region and an infrared absorber. It is preferable that the color material that shields light in the visible region contains two or more types of chromatic colorants, and forms black by a combination of two or more types of chromatic colorants. Alternatively, it is preferable that the colorant that blocks light in the visible region contains an organic black colorant. The organic black colorant is preferably at least one selected from perylene compounds and bisbenzofuranone compounds.

Description

Colored composition, film, color filter, pattern formation method, color filter manufacturing method, solid-state image sensor and infrared sensor

The present invention relates to a coloring composition. In particular, it relates to a colored composition preferably used in the production of a color filter. Further, it relates to a film using a colored composition, a color filter, a solid-state image sensor, and an infrared sensor. It also relates to a method for forming a pattern and a method for producing a color filter using a colored composition.

Solid-state imaging devices are utilized as optical sensors for various applications.

For example, since infrared rays have a longer wavelength than visible rays, they are difficult to be scattered, and can be used for distance measurement or three-dimensional measurement. In addition, since infrared rays are invisible to the eyes of humans and animals, the subject does not notice even when the subject is illuminated with an infrared light source at night, even when shooting nocturnal wild animals or for crime prevention purposes without irritating the other person. Can be used. As described above, an optical sensor (infrared ray sensor) that detects infrared rays can be developed for various purposes, and development of a film that can be used for an infrared sensor is desired.

Patent Document 1 discloses a coloring composition containing at least one of an azo-based yellow pigment or an isoindolin-based yellow pigment, and a pigment containing a dioxazine-based purple pigment.

In Patent Document 2, as a light-shielding photosensitive resin composition containing an alkali-soluble resin, a photoinitiator, an ethylenically unsaturated compound, and a light-shielding component, 95% or more of the light-shielding component is an organic pigment, and the organic pigment is the following (a From three or more of the groups) to (f), a light-shielding photosensitive resin composition is disclosed in which the standard deviation of the light transmittance in the range of 400 nm to 700 nm of the composition is 0.1% or less.

(a) Red pigment selected from Pigment Red 177, 209, 224, 254

(b) Pigment Blue 15:6 blue pigment

(c) a green pigment selected from Pigment Green 7, 36

(d) Pigment Yellow A yellow pigment selected from 83, 138, 139, 150, 180

(e) Pigment Violet 23 purple pigment

(f) an orange pigment selected from Pigment Orange 38, 71

In Patent Document 3, when a film having a film thickness of 1 μm is formed, the maximum value of the light transmittance in the thickness direction of the film in the range of 400 to 750 nm is 20% or less, and the light transmittance in the thickness direction of the film, the wavelength of 900 to 1300 nm A composition having a minimum value of 90% or more in the range of is described. In Patent Document 3, a red pigment, a yellow pigment, a blue pigment, and a pigment containing a purple pigment are used.

Patent Document 4 describes a near-infrared absorbing compound having absorption in the near-infrared region and excellent invisibility, which does not have absorption in the region of 400 to 700 nm.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-77009 Patent Document 2: Japanese Laid-Open Patent Publication No. 2009-69822 Patent Document 3: Japanese Laid-Open Patent Publication No. 2014-130338 Patent Document 4: Japanese Laid-Open Patent Publication No. 2009-263614

In recent years, development of an optical sensor using an infrared ray having a longer wavelength as a light source, such as an infrared ray having a wavelength of 900 nm or more, has been studied.

However, it has been found that in a film known so far as described in Patent Documents 1 to 3, etc., noise derived from visible light is liable to occur when applied to an optical sensor or the like using infrared rays having a wavelength of 900 nm or more as a light source.

On the other hand, in Patent Document 4, there is no disclosure or suggestion regarding a film capable of transmitting infrared rays in a state where there is little noise derived from visible light.

Accordingly, an object of the present invention is to provide a colored composition capable of forming a film capable of transmitting infrared rays in a state where noise derived from visible light is small. Another object of the present invention is to provide a film, a color filter, a pattern formation method, a color filter manufacturing method, a solid-state image sensor, and an infrared sensor using such a colored composition.

As a result of detailed investigation, the inventors of the present invention have found that the above problems can be achieved by using a coloring material that blocks light in the visible region and a coloring composition containing an infrared absorber, and the present invention has been completed. That is, the present invention is as follows.

<1> A coloring composition containing a coloring material that blocks light in the visible region and an infrared absorber.

<2> The coloring composition according to <1>, wherein the colorant for blocking light in the visible range contains two or more chromatic colorants, and forms black by a combination of two or more chromatic colorants.

<3> The coloring composition according to <1>, in which the color material for blocking light in the visible region contains an organic black colorant.

The coloring composition according to <3>, wherein the <4> organic black coloring agent is at least one selected from a perylene compound and a bisbenzofuranone compound.

The colored composition according to <4>, which further contains a <5> chromatic colorant.

The <6> chromatic colorant is the colored composition according to <2> or <5> selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.

The <7> infrared absorber is at least one selected from a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound, the coloring composition according to any one of <1> to <6> .

The coloring composition according to <7>, in which the <8> pyrrolopyrrole compound is a pigment.

The <9> pyrrolopyrrole compound is the coloring composition according to <7> or <8> represented by the following formula (1);

[Formula 1]

In formula (1), R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ are, They may be bonded to each other to form a ring, and R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, and R ⁴ represents R ^1a , R ^1b and At least one selected from R ³ may be a covalent bond or a coordination bond, and R ^4A and R ^4B each independently represent a hydrogen atom or a substituent.

The coloring composition in any one of <1>-<9> which contains a <10> polymeric compound further.

The coloring composition according to <10>, which further contains a <11> photoinitiator.

The coloring composition in any one of <1>-<11> used for manufacture of a <12> color filter.

<13> A film obtained by curing the colored composition according to any one of <1> to <12>.

<14> The color filter which has the film as described in <13>.

<15> The process of forming a colored composition layer on a support body using the colored composition in any one of <1> to <12>, the process of exposing the colored composition layer in a pattern shape, and developing and removing an unexposed part A pattern formation method comprising a step of forming a colored pattern.

<16> The manufacturing method of a color filter including the pattern formation method of <15>.

<17> A solid-state imaging device having the color filter according to <14>.

<18> Infrared sensor which has the color filter as described in <14>.

Advantageous Effects of Invention According to the present invention, it is possible to provide a colored composition capable of forming a film capable of transmitting infrared rays in a state with little noise derived from visible light. Moreover, a film, a color filter, a pattern formation method, a color filter manufacturing method, a solid-state imaging device, and an infrared sensor using such a colored composition can be provided.

1 is a schematic cross-sectional view showing a configuration of an embodiment of an infrared sensor of the present invention.
2 is a functional block diagram of an imaging device to which the infrared sensor of the present invention is applied.

In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the colored composition. Moreover, solid content means a solid content in 25 degreeC.

In the notation of the group (atomic group) in the present specification, the notation that does not describe substituted or unsubstituted includes not only having no substituent but also having a substituent. For example, the term "alkyl group" includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

The term "radiation" in the present specification means, for example, a bright ray spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV rays), X rays, electron rays, and the like. In addition, in the present invention, light means actinic ray or radiation. In the present specification, "exposure" refers to exposure using far ultraviolet rays, X-rays, EUV light, etc. typified by mercury lamps and excimer lasers, as well as drawing using particle rays such as electron beams and ion beams, unless otherwise specified. Include in

In the present specification, "(meth)acrylate" represents both or any one of acrylate and methacrylate, "(meth)acrylic" represents both or any one of acrylic and methacrylate, and "( "Meth) acryloyl" represents both or any one of acryloyl and methacryloyl.

In the present specification, in the formula, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In the present specification, the term "step" is included in the term as long as the desired action of the step is achieved, not only in an independent step, but also in a case where it cannot be clearly distinguished from other steps.

In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values in gel permeation chromatography (GPC) measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, TSKgel Super AWM-H (manufactured by Tosoh Corporation) using HLC-8220 (manufactured by Tosoh Corporation) as a column. , 6.0 mm ID (inner diameter) x 15.0 cm) can be obtained by using a 10 mmol/L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.

The pigment used in the present invention means an insoluble dye compound that is difficult to dissolve in a solvent. Typically, it means a dye compound present in a dispersed state as particles in the composition. Here, an arbitrary solvent is mentioned with a solvent, For example, the solvent illustrated in the column of a solvent mentioned later is mentioned. The pigment used in the present invention preferably has a solubility at 25° C. of 0.1 g/100 g or less in either of propylene glycol monomethyl ether acetate and water, for example.

<Coloring composition>

The colored composition of the present invention contains a colorant that blocks light in the visible region and an infrared absorber.

Since the colored composition of the present invention transmits infrared rays (preferably light having a wavelength of 900 nm or more), it can also be referred to as an infrared transmissive composition.

Hereinafter, each component that can constitute the colored composition of the present invention will be described.

<<infrared absorber>>

The colored composition of the present invention contains an infrared absorber.

In the present invention, the infrared absorber means a compound having an absorption maximum in the infrared region (preferably, the wavelength of 800 to 1300 nm).

The infrared absorber is preferably a compound having an absorption maximum in a wavelength range of 800 to 900 nm.

Although either a pigment or a dye may be used as an infrared absorber, a pigment is preferable because it is easy to obtain a colored composition capable of forming a film excellent in heat resistance. The pigment preferably has an average particle diameter (r) of 20 nm≦r≦300 nm, more preferably 25 nm≦r≦250 nm, and particularly preferably 30 nm≦r≦200 nm. In addition, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also simply referred to as “particle size distribution”) is that the secondary particles entering (average particle diameter ± 100) nm are not less than 70% by mass of the total, preferably 80 It is preferably not less than mass%. In addition, the average particle diameter of the primary particles can be determined by observing with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), measuring 100 particle sizes at a portion where particles are not aggregated, and calculating the average value. have.

As an infrared absorber, for example, a pyrrolopyrrole compound, a copper compound, a cyanine compound, a phthalocyanine compound, an iminium compound, a thiol complex system compound, a transition metal oxide compound, a squarylium compound, and a naphthalocyanine compound Compounds, quarterylene compounds, dithiol metal complex system compounds, and chromonium compounds.

As the phthalocyanine compound, naphthalocyanine compound, iminium compound, cyanine compound, squarylium compound, and chromonium compound, the compounds described in paragraphs 0010 to 0081 of JP 2010-111750 A may be used. , This content is intended to be incorporated in the present specification. In addition, for the cyanine compound, for example, reference can be made to the description of "functional pigment, Makoto Ogawara / Masaru Matsuoka / Daiiro Kitao / Tsuneaki Hirashima, work, Kodansha Scientific", the contents of which are in the present specification. It is assumed to be used.

In the present invention, as an infrared absorber, the compound described in paragraphs 0004 to 0016 of JP-A-07-164729 A, the compound described in paragraphs 0027 to 062 of JP 2002-146254, and JP 2011-164583 Near-infrared absorbing particles having a number average agglomerated particle diameter of 5 to 200 nm, which are composed of crystallites of an oxide containing Cu and/or P described in paragraphs 0034 to 0067 of the issue, may be used, and this content shall be incorporated herein by reference. Further, FD-25 (manufactured by Yamada Chemical Corporation), IRA842 (naphthalocyanine compound, manufactured by Exiton Corporation), and the like can also be used.

In the present invention, the infrared absorber is preferably at least one selected from a pyrrolopyrrole compound, a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound.

As a polymethine compound, a cyanine compound, a merocyanine compound, a squarylium compound, a chromonium compound, an oxonol compound, etc. are contained depending on the kind of the atomic group to which it is bonded. Among them, a cyanine compound, a squarylium compound, and an oxonol compound are preferable, and a cyanine compound and a squarylium compound are more preferable.

In the present invention, the infrared absorber may be a pigment or a dye.

<<<pyrrolopyrrole compound>>>

The pyrrolopyrrole compound may be a pigment or a dye, but a pigment is preferable because it is easy to obtain a colored composition capable of forming a film having excellent heat resistance.

As a pyrrolopyrrole compound, a compound represented by the following formula (1) is preferable. Excellent spectral properties can be obtained by using the compound represented by the following formula (1). In addition, a film excellent in heat resistance can be formed.

[Formula 2]

In formula (1), R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ are, They may be bonded to each other to form a ring, and R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, and R ⁴ represents R ^1a , R ^1b and At least one selected from R ³ may be a covalent bond or a coordination bond, and R ^4A and R ^4B each independently represent a hydrogen atom or a substituent.

In formula (1), as the alkyl group represented by R ^1a or R ^1b , it is preferably an alkyl group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example methyl, Ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, and the like. The alkyl group may have a substituent or may be unsubstituted. As a substituent, a substituent T mentioned later and a group represented by Formula A mentioned later are mentioned, for example.

The aryl group represented by R ^1a or R ^1b is preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenyl, orthomethylphenyl, para Methylphenyl, biphenyl, naphthyl, anthranyl, phenanthryl, and the like. The aryl group may have a substituent or may be unsubstituted. As a substituent, a substituent T mentioned later and a group represented by Formula A mentioned later are mentioned, for example.

The heteroaryl group represented by R ^1a or R ^1b is preferably a 5- or 6-membered ring. In addition, the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensation numbers, and still more preferably a monocyclic ring or a condensed ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example. As the heteroaryl group, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, naphthothiazolyl, benzoxazolyl , Metacarbazolyl, azepinyl, and the like. The heteroaryl group may have a substituent or may be unsubstituted. As a substituent, a substituent T mentioned later and a group represented by Formula A mentioned later are mentioned, for example.

The group represented by R ^1a and R ^1b is preferably an aryl group having an alkoxy group having a branched alkyl group. The number of carbon atoms of the branched alkyl group is preferably 3 to 30, and more preferably 3 to 20.

R ^1a and R ^1b in Formula (1) may be the same as or different from each other.

R ² and R ³ each independently represent a hydrogen atom or a substituent. R ² and R ³ may be bonded to each other to form a ring. At least one of R ² and R ³ is preferably an electron withdrawing group. It is preferable that R ² and R ³ each independently represent a cyano group or a heteroaryl group.

As the substituent, the substituents described in paragraphs 0020 to 0022 of JP 2009-263614A can be mentioned. In this specification, the above contents are used.

As an example of a substituent, the following substituent T is mentioned.

(Substituent T)

Alkyl group (preferably 1 to 30 carbon atoms. For example, methyl group, ethyl group, cyclohexyl group, etc.), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably 2 to 30 carbon atoms) Alkynyl group), aryl group (preferably aryl group having 6 to 30 carbon atoms. For example, phenyl group, paramethylphenyl group, biphenyl group, naphthyl group, etc.), amino group (preferably an amino group having 0 to 30 carbon atoms), alkoxy Group (preferably an alkoxy group having 1 to 30 carbon atoms. For example, a methoxy group, 2-ethylhexyloxy group, etc.), an aryloxy group (preferably an aryloxy group having 6 to 30 carbon atoms. For example, a phenyloxy group) , 1-naphthyloxy group, 2-naphthyloxy group, etc.), heteroaryloxy group (preferably a C1-C30 heteroaryloxy group. For example, a pyridyloxy group, etc.), an acyl group (preferably a C2 group) -30 acyl group), alkoxycarbonyl group (preferably C2-C30 alkoxycarbonyl group), aryloxycarbonyl group (preferably C7-C30 aryloxycarbonyl group), acyloxy group (preferably C2-C30 acyloxy group), acylamino group (preferably C2-C30 acylamino group), alkoxycarbonylamino group (preferably C2-C30 alkoxycarbonylamino group), aryloxycarbonylamino group ( Preferably, an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfonylamino group (preferably a sulfonyl amino group having 1 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), carba Moyl group (preferably a carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), Heteroarylthio group (preferably C1-C30 heteroarylthio group), alkylsulfinyl group (preferably C1-C30 alkylsulfinyl group), arylsulfinyl group (preferably C6-C30 arylsulfin) Diary), alkyl ureido group (preferably an alkyl ureido group having 1 to 30 carbon atoms), aryl ureido group (preferably an aryl ureido group having 6 to 30 carbon atoms), phosphate amide group (preferably, phosphoric acid having 1 to 30 carbon atoms) Amide group), hydroxy Group, mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), cyano group, sulfo group, carboxy group, nitro group, hydroxamic acid group, sulfino group, Hydrazino group, imino group, heteroaryl group.

When these groups are a group which can be substituted further, they may further have a substituent. As a substituent, a group represented by the said substituent T and a group represented by following formula A is mentioned.

A: -L ¹ -X ¹

In the formula, L ¹ represents a single bond or a divalent linking group, and X ¹ represents a (meth)acryloyloxy group, an epoxy group, an oxetanyl group, an isocyanate group, a hydroxy group, an amino group, a carboxyl group, a thiol group , An alkoxysilyl group, a methylol group, a vinyl group, a (meth)acrylamide group, a sulfo group, a styryl group, or a maleimide group.

When L ¹ represents a divalent linking group, L ¹ represents an alkylene group having 2 to 20 carbon atoms, an arylene group having 6 to 18 carbon atoms, a heteroarylene group having 3 to 18 carbon atoms, -O-, -S-, -C( =O)-, or a group consisting of a combination of these groups is preferred.

X ¹ is more preferably one or more selected from a (meth)acryloyloxy group, a vinyl group, an epoxy group and an oxetanyl group, and more preferably a (meth)acryloyloxy group.

At least one of R ² and R ³ is preferably an electron withdrawing group. A substituent whose σp value (sigma para value) of Hammett is positive acts as an electron withdrawing group.

In the present invention, a substituent having a Hammett σp value of 0.2 or more can be illustrated as an electron withdrawing group. As a σp value, it is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less.

As specific examples, a cyano group (σp value = 0.66), a carboxy group (-COOH: σp value = 0.45), an alkoxycarbonyl group (-COOMe: 0.45), an aryloxycarbonyl group (e.g. -COOPh: σp value = 0.44) ), carbamoyl group (e.g. -CONH ₂ : σp value = 0.36), alkylcarbonyl group (e.g. -COMe: σp value = 0.50), arylcarbonyl group (e.g. -COPh: σp value = 0.43) , An alkylsulfonyl group (eg -SO ₂ Me: σp value = 0.72), an arylsulfonyl group (eg -SO ₂ Ph: σp value = 0.68), and the like. Especially preferably, it is a cyano group. Here, Me represents a methyl group and Ph represents a phenyl group.

Regarding the Hammett's substituent constant σ value, for example, paragraphs 0017 to 0018 of JP-A-2011-68731 A can be referred to, and this content is assumed to be incorporated herein.

When R ² and R ³ are bonded to form a ring, a 5 to 7 membered ring (preferably a 5 to 6 membered ring) is formed, and the formed ring is usually used as an acidic nucleus in a merocyanine dye. desirable. As a specific example, the structure described in Paragraph No. 0026 of Japanese Unexamined Patent Application Publication No. 2009-263614 is mentioned, and this content is intended to be incorporated in this specification.

In addition, the σp value of R ² and R ³ in the case of forming a ring cannot be defined, but in the present invention, it is assumed that the partial structure of the ring is substituted for R ² and R ³ respectively, and the σp value in the case of ring formation Is defined as For example, in the case of forming a 1,3-indenedion ring, it is considered that R ² and R ³ are each substituted with a benzoyl group.

As the ring formed by bonding of R ² and R ³ , preferably 1,3-dicarbonyl nucleus, pyrazolinone nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone bodies), 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4 -Thyazolidinedione nucleus, 2,4-imidazolidinedione nucleus, 2-thio-2,4-imidazolidinedione nucleus, 2-imidazoline-5-one nucleus, 3,5-pyra It is a zolidindione nucleus, a benzothiophen-3-one nucleus, or an indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body) ), 3,5-pyrazolidinedione nucleus, benzothiophen-3-one nucleus, or indanone nucleus.

It is particularly preferred that R ³ is a heteroaryl group. The heteroaryl group is preferably a 5- or 6-membered ring. In addition, the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensation numbers, and still more preferably a monocyclic ring or a condensed ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, and more preferably 1 to 2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example. As a heteroaryl group, it is preferable that it is a quinoline group, a benzothiazole group, or a naphthothiazole group, and a benzothiazole group is more preferable. The heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the above-described substituent T and the group represented by the above-described formula A.

Two R ² in Formula (1) may be the same or different from each other, and two R ³ may be the same or different from each other.

When R ⁴ represents an alkyl group, an aryl group, or a heteroaryl group, the alkyl group, aryl group, and heteroaryl group are the same as those described for R ^1a and R ^1b , and the preferred range is also the same.

When R ⁴ represents -BR ^4A R ^4B , R ^4A and R ^4B each independently represent a hydrogen atom or a substituent, and R ^4A and R ^4B may be bonded to each other to form a ring. Examples of the substituent represented by R ^4A and R ^4B include the aforementioned substituent T, preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group. And an aryl group are particularly preferred. Specific examples of the group represented by -BR ^4A R ^4B include difluoro boron, diphenyl boron, dibutyl boron, dyafthyl boron, and catechol boron. Among them, diphenyl boron is particularly preferred.

When R ⁴ represents a metal atom, examples of the metal atom include magnesium, aluminum, calcium, barium, zinc, tin, tin, vanadium, iron, cobalt, nickel, copper, palladium, iridium, and platinum, and aluminum and zinc. , Vanadium, iron, copper, palladium, iridium and platinum are particularly preferred.

R ⁴ may be covalently bonded or covalently bonded to at least one of R ^1a , R ^1b, and R ³ , and it is particularly preferable that R ⁴ is covalently bonded to R ³ .

It is preferable that R ^{4 is a} hydrogen atom or a group represented by -BR ^4A R ^4B (especially diphenyl boron).

Two R ⁴ in Formula (1) may be the same or different from each other.

The compound represented by formula (1) is preferably a compound represented by any one of the following formulas (2), (3) or (4).

[Formula 3]

In formula (2), Z ^1a and Z ^1b each independently represent an atomic group forming an aryl ring or heteroaryl ring. R ^5a and R ^5b are each independently an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, A carboxy group, a carbamoyl group having 1 to 20 carbon atoms, a halogen atom, or a cyano group may be represented, and R ^5a or R ^5b and Z ^1a or Z ^1b may be bonded to each other to form a condensed ring. R ²² and R ²³ are each independently a cyano group, an acyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfinyl group having 1 to 10 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, or A nitrogen-containing heteroaryl group having 3 to 20 carbon atoms is shown. R ²² and R ²³ may be bonded to each other to form a cyclic acidic nucleus. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, -BR ^4A R ^4B , or a metal atom, and a covalent bond or a coordination bond with R ²³ You may have. R ^4A and R ^4B each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 4 to 20 carbon atoms. .

In formula (2), Z ^1a and Z ^1b each independently represent an atomic group forming an aryl ring or a heteroaryl ring. The formed aryl ring and heteroaryl ring have the same meaning as the aryl group and heteroaryl group described as the substituents for R ² and R ^{3 in} the formula (1), and the preferred ranges are also the same. It is preferred that Z ^1a and Z ^1b are the same.

R ^5a and R ^5b have the same definition as the examples described for R ² and R ³ in the formula (1), and the preferred ranges are also the same. R ^5a and R ^5b are preferably the same.

R ^5a or R ^5b and Z ^1a or Z ^1b may be bonded to each other to form a condensed ring, and examples of such a condensed ring include a naphthyl ring and a quinoline ring. Invisibility can be greatly improved by introducing a group represented by R ^5a or R ^5b into the aryl ring or heteroaryl ring formed by Z ^1a or Z ^1b .

R ²² and R ²³ have the same meaning as the examples described for R ² and R ³ in the formula (1), and the preferred ranges are also the same.

R ⁴ is R ⁴ and agreement in the formula (1), are also the same preferable range. R ⁴ may have a covalent bond or a coordination bond with R ²³ .

The compound represented by formula (2) may further have a substituent, and the substituent is synonymous with the substituent of R ² and R ³ , and the preferred range is also the same.

As a preferable combination in formula (2), Z ^1a and Z ^1b each independently form a benzene ring or a pyridine ring, and R ^5a and R ^5b are each independently an alkyl group, an alkoxy group, a halogen atom or between An ano group, R ²² and R ²³ are each independently a heteroaryl group, a cyano group, an acyl group, an alkoxycarbonyl group, or a cyclic acidic nucleus bonded to R ²² and R ²³ , and R ⁴ is a hydrogen atom, -BR ^4A R ^4B , transition metal atom, magnesium, aluminum, calcium, barium, zinc or tin. As a particularly preferred combination, both Z ^1a and Z ^1b form a benzene ring, R ^5a and R ^5b are both an alkyl group, a halogen atom, or a cyano group, and R ²² and R ²³ are each independently nitrogen-containing hetero A combination of an aryl group and a cyano group or an alkoxycarbonyl group, or a cyclic acidic nucleus in which R ²² and R ²³ are bonded, and R ⁴ is a hydrogen atom, -BR ^4A R ^4B , aluminum, zinc, vanadium, iron, copper, palladium, This is the case with iridium and platinum.

[Formula 4]

In formula (3), R ^31a and R ^31b each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ³² is a cyano group, an acyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfinyl group having 1 to 10 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, or a nitrogen-containing nitrogen having 3 to 10 carbon atoms Represents a heteroaryl group. R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a heteroaryl group having 4 to 10 carbon atoms. R ⁶ and R ⁷ may be bonded to each other to form a condensed ring, and the ring to be formed is preferably an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, or a heteroaryl ring having 3 to 10 carbon atoms. Each of R ⁸ and R ⁹ independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms. X represents an oxygen atom, a sulfur atom, -NR-, -CRR'-, and R and R'represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

In formula (3), R ^31a and R ^31b have the same ^meaning as the examples described for R ^1a and R ^1b in formula (1), and the preferred ranges are also the same. R ^31a and R ^31b are preferably the same.

R ³² is synonymous with the example of R ² in formula (1), and the preferred range is also the same.

R ⁶ and R ⁷ have the same meaning as the examples of the substituents of R ² and R ^{3 in} the formula (1), and their preferred ranges are also the same. Further, R ⁶ and R ⁷ may be bonded to form a ring, and the ring to be formed is an alicyclic ring having 5 to 10 carbon atoms, an aryl ring having 6 to 10 carbon atoms, and a heteroaryl ring having 3 to 10 carbon atoms, and preferred examples include a benzene ring or naphthalene. Ring, pyridine ring, etc. are mentioned. By introducing a 5-membered nitrogen-containing heteroaryl ring substituted with R ⁶ and R ⁷ and forming a boron complex, it is possible to realize an infrared absorbing dye that is compatible with high fastness and high invisibility.

R ⁸ and R ⁹ have the same meaning as the examples of the substituents of R ² and R ^{3 in} the formula (1), and the preferred ranges are also the same.

X represents an oxygen atom, a sulfur atom, -NR-, or -CRR'-. R and R'each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group.

As a preferable combination in formula (3), R ^31a and R ^31b are each independently an alkyl group having 1 to 10 carbon atoms, a benzene ring or a pyridine ring, R ³² is a cyano group or an alkoxycarbonyl group, and R ⁶ and R ⁷ is bonded to form a benzene ring, a pyridine ring, a pyrazine ring, or a pyrimidine ring, R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group, X is an oxygen atom, sulfur An atom, -NR-, -CRR'-, and R and R'are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group. As a particularly preferred combination, R ^31a and R ^31b are both an alkyl group or a benzene ring having 1 to 10 carbon atoms, R ³² is a cyano group, R ⁶ and R ⁷ are bonded to form a benzene ring or a pyridine ring, and R ⁸ and R ⁹ are each independently an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a naphthyl group, and X is oxygen or sulfur.

[Formula 5]

In formula (4), R ^41a and R ^41b represent different groups, and represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms. R ⁴² is a cyano group, an acyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfinyl group having 1 to 10 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, or a nitrogen-containing nitrogen having 3 to 10 carbon atoms Represents a heteroaryl group. Z ² represents an atomic group forming a nitrogen-containing 5 or 6-membered ring together with -C=N-, and examples of the nitrogen-containing heteroaryl ring include a pyrazole ring, a thiazole ring, an oxazole ring, an imidazole ring, an oxadiazole ring, and a thia A diazole ring, a triazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a benzo-condensed ring or a naphtho-condensed ring, or a complex of these condensed rings is shown. R ⁴⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, a heteroaryl group having 4 to 20 carbon atoms, -BR ^44A R ^44B , or a metal atom, and R ⁴⁴ is formed by Z ² May have a nitrogen-containing heterocycle and a covalent bond or a coordination bond, and R ^44A and R ^44B are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 4 It represents a heteroaryl group of ~20.

In formula (4), R ^41a and R ^41b have the same ^definition as the examples described for R ^1a and R ^1b in formula (1), and the preferred ranges are also the same. However, R ^41a and R ^41b represent different groups.

R ⁴² has the same meaning as the example of R ^{2 in} the formula (1), and the preferred range is also the same.

Z ² represents an atomic group forming a nitrogen-containing hetero 5 or 6 membered ring together with -C=N-, and examples of the nitrogen-containing heteroaryl ring include a pyrazole ring, a thiazole ring, an oxazole ring, an imidazole ring, an oxadiazole ring, and a thi. An adiazole ring, a triazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a benzo-condensed ring or a naphtho-condensed ring, or a complex of these condensed rings is shown.

R ⁴⁴ is a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aryl group, a C4-C20 heteroaryl group, a metal atom, or as a substituent, a halogen atom, a C1-C10 alkyl group, a C6 Represents an aryl group of ~ 20, -BR ^44A R ^44B , or a metal atom, R ⁴⁴ may have a covalent bond or a coordination bond with the nitrogen-containing heterocycle formed by Z ² , and R4 ^4A and R ^44B are each independently As a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 4 to 20 carbon atoms.

By introducing different groups represented by R ^41a and R ^41b , and introducing a nitrogen-containing hetero 5 or 6-membered ring in which Z ² forms with -C=N-, high fastness, high invisibility, excellent dispersibility, and high organic Solvent solubility can be imparted.

As a preferable combination in formula (4), R ^41a and R ^41b are each independently an alkyl group having 1 to 10 carbon atoms, a benzene ring or a pyridine ring, and R ⁴² is a cyano group, an alkyl or aryl having 1 to 10 carbon atoms. A sulfinyl group or an alkoxycarbonyl group, and Z ² is a thiazole ring, an oxazole ring, an imidazole ring, a thiadiazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, together with -C=N- These benzo condensed rings or naphtho condensed rings are formed, and R ⁴⁴ is a hydrogen atom, -BR ^44A R ^44B , a transition metal atom, magnesium, aluminum, calcium, barium, zinc, or tin. As a particularly preferred combination, R ^41a and R ^41b are each independently an alkyl group or a benzene ring having 1 to 10 carbon atoms, R ⁴² is a cyano group, and Z ² is a thiazole ring or an oxazole ring together with -C=N- , An imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, or a benzo-condensed ring or a naphtho-condensed ring thereof, and R ⁴⁴ is a hydrogen atom, -BR ^44A R ^44B (as R ^44A and R ^44B , each independently This is the case in the case of an alkyl group having 1 to 10 carbon atoms, a benzene ring, a pyridine ring, or a thiophene ring), aluminum, zinc, vanadium, iron, copper, palladium, iridium, or platinum.

The pyrrolopyrrole compound is particularly preferably a compound represented by the following formula (5).

[Formula 6]

In formula (5), R ⁵¹ to R ⁵⁴ each independently represent a substituent,

R ⁵⁵ to R ⁵⁶ are each independently a cyano group, an acyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfinyl group having 1 to 10 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, or Represents a nitrogen-containing heteroaryl group having 3 to 10 carbon atoms,

R ^57a to R ^57d each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms,

n1 and n2 each independently represent an integer of 0-5,

n3 and n4 each independently represent the integer of 0-4.

The substituents represented by R ⁵¹ and R ⁵² include the substituents described for the above-described substituent T.

R ⁵¹ and R ⁵² are each independently an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, a halogen atom or a cyano group, more preferably an alkoxy group or an aryloxy group, and particularly an alkoxy group desirable.

The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20. The alkyl group may be linear, branched, or cyclic, and linear or branched is preferable.

The number of carbon atoms of the aryl group and the aryloxy group is preferably 6 to 30, more preferably 6 to 20.

1-30 are preferable and, as for the carbon number of an alkoxy group, 1-20 are more preferable. The alkoxy group is preferably linear or branched, and more preferably branched.

The heteroaryl ring possessed by the heteroaryloxy group is preferably a 5- or 6-membered ring. Further, the heteroaryl ring is preferably a monocyclic or condensed ring, more preferably a monocyclic or condensed ring having 2 to 8 condensation numbers, and more preferably a monocyclic or condensed ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the heteroaryl ring is preferably 1 to 3, and more preferably 1 to 2. As a hetero atom, a nitrogen atom, an oxygen atom, and a sulfur atom are illustrated, for example.

The substituents represented by R ⁵³ and R ⁵⁴ include the substituents described for the above-described substituent T.

R ⁵³ and R ⁵⁴ are each independently preferably an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, a halogen atom or a cyano group.

R ⁵⁵ to R ⁵⁶ are each independently a cyano group, an acyl group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkylsulfinyl group having 1 to 10 carbon atoms, an arylsulfinyl group having 6 to 10 carbon atoms, or A nitrogen-containing heteroaryl group having 3 to 10 carbon atoms is represented, and a cyano group is preferable.

R ^57a to R ^57d each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a heteroaryl group having 3 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms Or a C6-C20 aryl group is preferable, a C6-C20 aryl group is more preferable, and a phenyl group is especially preferable.

Each of n1 and n2 independently represents the integer of 0-5, 0-3 are preferable, 0-2 are more preferable, and 1 is especially preferable. Particularly preferred are combinations in which n1 and n2 are 1 and R ⁵¹ and R ⁵² are alkoxy groups.

Each of n3 and n4 independently represents the integer of 0-4, and 0-2 are preferable.

As a specific example of the compound represented by Formula (1), the following compounds are mentioned, for example. Further, the compounds described in paragraphs 0049 to 0058 of JP 2009-263614A can be mentioned.

[Formula 7]

<<<phthalocyanine compound>>>

As for the phthalocyanine compound, oxo titanylphthalocyanine and vanadium phthalocyanine are preferable.

The oxo titanylphthalocyanine is preferably a compound represented by the following formula (PC).

[Formula 8]

In the formula, X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom.

In X ¹ to X ¹⁶ , 0 to 16 are preferable, as for the number of halogen atoms, 0 to 4 are more preferable, 0 to 1 are more preferable, and 0 is particularly preferable.

The oxo titanylphthalocyanine may be any of α-type, β-type, and Y-type, but α-type is preferable from the viewpoint of spectroscopy.

The vanadium phthalocyanine is preferably a compound represented by the following formula (PC-1).

[Formula 9]

In the formula, X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom.

In X ¹ to X ¹⁶ , 0 to 16 are preferable, as for the number of halogen atoms, 0 to 4 are more preferable, 0 to 1 are more preferable, and 0 is particularly preferable.

<<<Naphthalocyanine compound>>>

As for the naphthalocyanine compound, oxovanadilnaphthalocyanine is preferable.

Oxovanadyl naphthalocyanine is preferably a compound represented by the following formula (NPC).

[Formula 10]

In the formula, X ¹ to X ²⁴ each independently represent a hydrogen atom or a halogen atom.

In X ¹ to X ²⁴ , 0 to 24 are preferable, as for the number of halogen atoms, 0 to 4 are more preferable, 0 to 1 are more preferable, and 0 is particularly preferable.

<<<Squararylium compound>>>

The squarylium compound is preferably a compound represented by the following formula (SQ).

[Formula 11]

In formula (SQ), A ¹ and A ² each independently represent an aryl group, a heterocyclic group, or a group represented by the following formula (sq1).

[Formula 12]

In formula (sq1), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and a broken line is It represents the connecting hand with formula (SQ).

A ¹ and A ² in formula (SQ) each independently represent an aryl group, a heterocyclic group, or a group represented by formula (sq1), and a group represented by formula (sq1) is preferable.

The number of carbon atoms in the aryl group represented by A ¹ and A ² is preferably 6 to 48, more preferably 6 to 24, and particularly preferably 6 to 12. As a specific example, a phenyl group, a naphthyl group, etc. are mentioned. In addition, in the case where the aryl group has a substituent, the number of carbon atoms of the aryl group means the number excluding the number of carbon atoms of the substituent.

As the heterocyclic group represented by A ¹ and A ² , a 5- or 6-membered ring is preferable. In addition, the heterocyclic group is preferably a monocyclic or condensed ring, more preferably a monocyclic or condensed ring having 2 to 8 condensation numbers, more preferably a monocyclic or condensed ring having 2 to 4 condensation numbers, and condensation having 2 or 3 condensation numbers Rings are particularly preferred. As the hetero atom contained in the heterocyclic group, a nitrogen atom, an oxygen atom, and a sulfur atom are exemplified, and a nitrogen atom and a sulfur atom are preferable. As for the number of hetero atoms, 1-3 are preferable, and 1-2 are more preferable. Specifically, a heterocyclic group derived from a monocyclic or polycyclic aromatic ring such as a 5- or 6-membered ring containing at least one of a nitrogen atom, an oxygen atom and a sulfur atom may be mentioned.

The aryl group and the heterocyclic group may have a substituent. As a substituent, a halogen atom, a hydroxy group, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, aryloxy group, heteroaryloxy group, Alkylthio, arylthio, heteroarylthio, -NR ^a1 R ^a2 , -COR ^a3 , -COOR ^a4 , -OCOR ^a5 , -NHCOR ^a6 , -CONR ^a7 R ^a8 , -NHCONR ^a9 R ^a10 , -NHCOOR ^a11 , -SO ₂ R ^a12 , -SO ₂ OR ^a13 , -NHSO ₂ R ^a14 or -SO ₂ NR ^a15 R ^a16 . Each of R ^a1 to R ^a16 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of carbon atoms of the alkyl group, alkoxy group and arylthio group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and linear or branched is preferable.

As for the carbon number of an alkenyl group, 2-20 are preferable, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic, and linear or branched is preferable.

The number of carbon atoms of the alkyneyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkynyl group may be linear, branched or cyclic, and linear or branched is preferable.

The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 12.

The aryl groups that the aryloxy group and the arylthio group have include those described above, and the preferred ranges are also the same.

The alkyl moiety of the aralkyl group is the same as the alkyl group. The aryl moiety of the aralkyl group is the same as the aryl group. The number of carbon atoms of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.

The heteroaryl group is preferably a monocyclic or condensed ring, preferably a monocyclic or condensed ring having 2 to 8 condensation numbers, and more preferably a monocyclic or condensed ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The heteroaryl group is preferably a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.

The heteroaryl groups of the heteroaryloxy group and the heteroarylthio group include those described above, and the preferred ranges are also the same.

As for the substituent which the aryl group and the heterocyclic group may have, a halogen atom, an alkyl group, a hydroxy group, -NR ^a1 R ^a2 and -NHCOR ^a6 are preferable.

When the aryl group and the heterocyclic group have two or more substituents, a plurality of substituents may be the same or different.

Next, a group represented by the formula (sq1) represented by A ¹ and A ² will be described.

[Formula 13]

In formula (sq1), Z ¹ represents a non-metal atom group forming a nitrogen-containing heterocycle, R ² represents an alkyl group, an alkenyl group or an aralkyl group, d represents 0 or 1, and the broken line represents the formula (SQ ) Represents the connecting hand.

In formula (sq1), R ² represents an alkyl group, an alkenyl group or an aralkyl group, and an alkyl group is preferable.

The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 12, and particularly preferably 2 to 8.

The number of carbon atoms of the alkenyl group is preferably 2 to 30, more preferably 2 to 20, and still more preferably 2 to 12.

The alkyl group and the alkenyl group may be linear, branched, or cyclic, and linear or branched is preferable.

7-30 are preferable and, as for the carbon number of an aralkyl group, 7-20 are more preferable.

In formula (sq1), as the nitrogen-containing heterocycle formed by Z ¹ , a 5-membered ring or a 6-membered ring is preferable. In addition, the nitrogen-containing heterocycle is preferably a monocyclic or condensed ring, more preferably a monocyclic or condensed ring having 2 to 8 condensation number, more preferably a monocyclic or condensed ring having 2 to 4 condensation number, and a condensed ring having 2 or 3 condensation number. It is particularly preferred. The nitrogen-containing heterocycle may contain a sulfur atom other than a nitrogen atom. Moreover, the nitrogen-containing heterocycle may have a substituent. As a substituent, the substituent which the aryl group or heterocyclic group mentioned above may have is mentioned, and the preferable range is also the same. For example, a halogen atom, an alkyl group, a hydroxy group, an amino group, and an acylamino group are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 12. The alkyl group is preferably linear or branched.

The group represented by the formula (sq1) is preferably a group represented by the following formula (sq2) or (sq3).

[Formula 14]

In formulas (sq2) and (sq3), R ¹¹ represents an alkyl group, an alkenyl group or an aralkyl group, and R ¹² represents a substituent, and when m is 2 or more, R ¹² may be connected to form a ring. And X represents a nitrogen atom or CR ¹³ R ¹⁴ , R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent, m represents an integer of 0 to 4, and the broken line represents the formula (SQ) It represents the connecting hand with

R ¹¹ in formulas (sq2) and (sq3) has the same meaning as R ² in formula (sq1), and the preferred range is also the same.

R ¹² in formulas (sq2) and (sq3) represents a substituent. As a substituent, the substituent which the above-mentioned aryl group or heterocyclic group may have is mentioned. For example, a halogen atom, an alkyl group, a hydroxy group, -NR ^a1 R ^a2 and -NHCOR ^a6 are preferable, and a halogen atom and an alkyl group are more preferable. The halogen atom is preferably a chlorine atom. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and still more preferably 1 to 12. The alkyl group is preferably linear or branched.

When m is 2 or more, R ¹² may be connected to each other to form a ring. Examples of the ring include an alicyclic (non-aromatic hydrocarbon ring), an aromatic ring, and a heterocyclic ring. The ring may be monocyclic or may be bicyclic. When the substituents are connected to each other to form a ring, as a linking group, -CO-, -O-, -NH-, a divalent aliphatic group, a divalent aromatic group, and a divalent linking group selected from the group consisting of a combination thereof I can. For example, it is preferable that R ¹² are connected to each other to form a benzene ring.

X in formula (sq2) represents a nitrogen atom or CR ¹³ R ¹⁴ , and R ¹³ and R ¹⁴ each independently represent a hydrogen atom or a substituent. As a substituent, the substituent which the above-mentioned aryl group or heterocyclic group may have is mentioned. For example, an alkyl group etc. are mentioned. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, more preferably 1 to 5, particularly preferably 1 to 3, and most preferably 1. The alkyl group is preferably linear or branched, and particularly preferably linear.

m represents the integer of 0-4, and 0-2 are preferable.

The squarylium compound is preferably a compound represented by the following formula (SQ-1).

Equation (SQ-1)

[Formula 15]

In formula (SQ-1), ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring,

X ^A and X ^B each independently represent a substituent,

G ^A and G ^B each independently represent a substituent,

kA represents an integer of 0 to nA, kB represents an integer of 0 to nB,

nA represents the maximum integer substitutable for ring A, nB represents the maximum integer substitutable for ring B,

X ^A and G ^A , X ^B and G ^B may be bonded to each other to form a ring, and when a plurality of G ^A and G ^B are each present, they may be bonded to each other to form a ring;

G ^A and G ^B each independently represent a substituent. As a substituent, the substituent which the above-mentioned aryl group or heterocyclic group may have is mentioned.

X ^A and X ^B each independently represent a substituent. The substituent is preferably a group having an active hydrogen, -OH, -SH, -COOH, -SO ₃ H, -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -NHSO ₂ R ^X1 , -B(OH) ₂ and -PO(OH) ₂ are more preferable, -OH, -SH and -NR ^X1 R ^X2 are more preferable, and -NR ^X1 R ^X2 are particularly preferable. .

R ^X1 and R ^X1 each independently represent a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an alkyneyl group, an aryl group, or a heteroaryl group. The details of the alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group are the same as those described for the substituents which the aryl group or heterocyclic group may have.

Ring A and ring B each independently represent an aromatic ring or a heteroaromatic ring. The aromatic ring and the heteroaromatic ring may be monocyclic or may be a condensed ring. Specific examples of the aromatic ring and the heteroaromatic ring include a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptalene ring, an indenene ring, a perylene ring, a pentaxene ring, an acenaphthene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring, and Sen ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, indole Lysine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolizin ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring , A phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromane ring, a xanthene ring, a phenoxacyine ring, a phenothiazine ring, and a phenazine ring, and a benzene ring or a naphthalene ring is preferable. The aromatic ring may be unsubstituted or may have a substituent. As a substituent, the substituent which the above-mentioned aryl group or heterocyclic group may have is mentioned.

X ^A and G ^A and X ^B and G ^B may be bonded to each other to form a ring. Moreover, when a plurality of G ^A exist, G ^A may be bonded to each other to form a ring. Moreover, when a plurality of G ^Bs exist, G ^Bs may be bonded to each other to form a ring.

As a ring, a 5-membered ring or a 6-membered ring is preferable. The ring may be monocyclic or may be bicyclic.

When X ^A and G ^A , X ^B and G ^B , G ^A or G ^B are bonded to each other to form a ring, they may be directly bonded to form a ring, and an alkylene group, -CO-, -O-,- A ring may be formed by bonding through a divalent linking group selected from the group consisting of NH-, -BR-, and combinations thereof. It is preferable that X ^A and G ^A , X ^B and G ^B , G ^A or G ^B are bonded to each other through -BR- to form a ring.

R represents a hydrogen atom or a substituent. Examples of the substituent include the substituents described for G ^A and G ^B.

kA represents an integer of 0 to nA, kB represents an integer of 0 to nB, nA represents the largest integer that can be substituted for ring A, and nB represents the maximum integer that can be substituted for ring B.

As for kA and kB, 0-4 are each independently preferable, 0-2 are more preferable, and 0-1 are especially preferable.

The following are mentioned as a specific example of a squarylium compound. In addition, the compounds described in paragraphs 0044 to 0049 of JP 2011-208101 A, and the compounds described in paragraphs 0072 to 0079 of JP 2015-40895 A are exemplified, the contents of which are incorporated herein by reference. .

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

<<<cyanine compound>>>

The cyanine compound is preferably a compound represented by the following formula (10).

Equation (10)

[Formula 22]

In the formula, Z ¹ and Z ² are each independently a group of non-metal atoms forming a 5- or 6-membered nitrogen-containing heterocycle which may be independently condensed,

R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,

L ¹ represents a meta-print consisting of an odd number of meta-popular groups,

a and b are each independently 0 or 1,

When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond,

When the moiety represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary to balance the charge, and when the moiety represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c Represents the number necessary to balance the charge, and c is 0 when the charge at the site represented by Cy in the formula is neutralized in the molecule.

Z ¹ and Z ² each independently represent a non-metallic group of atoms forming a 5- or 6-membered nitrogen-containing heterocycle which may be independently condensed.

In the nitrogen-containing heterocycle, other heterocycles, aromatic rings, or aliphatic rings may be condensed. The nitrogen-containing heterocycle is preferably a 5-membered ring. A structure in which a benzene ring or a naphthalene ring is condensed with a 5-membered nitrogen-containing heterocycle is more preferable. Specific examples of the nitrogen-containing heterocycle include oxazole ring, isoxazole ring, benzoxazole ring, naphthooxazole ring, oxazolocarbazole ring, oxazolodibenzofuran ring, thiazole ring, benzothiazole ring, naphthothiazole Ring, indolenine ring, benzoindolenine ring, imidazole ring, benzimidazole ring, naphthoimidazole ring, quinoline ring, pyridine ring, pyrrolopyridine ring, propyrol ring, indolizine ring, imidazoquinoxaline ring, quinox Saline ring, etc., and a quinoline ring, an indolenine ring, a benzoindolenine ring, a benzoxazole ring, a benzothiazole ring, and a benzimidazole ring are preferable, and an indolenine ring, a benzothiazole ring, and a benzimidazole ring are particularly desirable.

The nitrogen-containing heterocycle and the ring condensed thereto may have a substituent. As a substituent, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, -OR ^c1 , -COR ^c2 , -COOR ^c3 , -OCOR ^c4 , -NR ^c5 R ^c6 , -NHCOR ^c7 , -CONR ^c8 R ^c9 , -NHCONR ^c10 R ^c11 , -NHCOOR ^c12 , -SR ^c13 , -SO ₂ R ^c14 , -SO ₂ OR ^c15 , -NHSO ₂ R ^c16 or -SO ₂ NR ^c17 R ^c18 is mentioned. Each of R ^c1 to R ^c18 independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. Further, when R ^{c3 in} -COOR ^c3 is a hydrogen atom (ie, a carboxy group), the hydrogen atom may be dissociated (ie, a carbonate group) or may be in a salt state. In addition, when R ^c15 is a hydrogen atom of the -SO ₂ OR ^c15 (i.e., a sulfo) is, and may be dissociated hydrogen atoms (i.e., the sulfonate group), or may be a salt state.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched or cyclic. The alkyl group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group, and a carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may have a hydrogen atom dissociated or may be in a salt state.

As for the carbon number of an alkenyl group, 2-20 are preferable, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic. The alkenyl group may be unsubstituted or may have a substituent. As a substituent, the substituent which the above-mentioned alkyl group may have is mentioned, and the preferable range is also the same.

The number of carbon atoms of the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkyneyl group may be either linear or branched. The alkynyl group may be unsubstituted or may have a substituent. As a substituent, the substituent which the above-mentioned alkyl group may have is mentioned, and the preferable range is also the same.

The number of carbon atoms of the aryl group is preferably 6 to 25, more preferably 6 to 15, and most preferably 6 to 10. The aryl group may be unsubstituted or may have a substituent. As a substituent, the substituent which the above-mentioned alkyl group may have is mentioned, and the preferable range is also the same.

The alkyl moiety of the aralkyl group is the same as the alkyl group. The aryl moiety of the aralkyl group is the same as the aryl group. The number of carbon atoms of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.

The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensation numbers, and more preferably a monocyclic ring or a condensed ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The heteroaryl group may be unsubstituted or may have a substituent. As a substituent, the substituent which the above-mentioned alkyl group may have is mentioned, and the preferable range is also the same.

R ¹⁰¹ and R ¹⁰² each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group. The alkyl group, alkenyl group, alkynyl group, aralkyl group, and aryl group include those described for the above substituents, and the preferred ranges are also the same. The alkyl group, alkenyl group, alkynyl group, aralkyl group, and aryl group may have a substituent or may be unsubstituted. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group, and a carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may have a hydrogen atom dissociated or may be in a salt state.

L ¹ represents a metaprint consisting of an odd number of metapopular groups. L ¹ is preferably meta-printing consisting of 3, 5 or 7 meta-popular groups.

The meta-popular group may have a substituent. It is preferable that the metaphosphorus group which has a substituent is a central (meso-position) metaphosphorus group. As a specific example of a substituent, the substituent which the nitrogen-containing heterocycle of Z ¹ and Z ² may have, and a group represented by the following formula (a) are mentioned. Further, two substituents of metaprint may be bonded to form a 5 or 6 membered ring.

[Formula 23]

In formula (a), * represents a connection part with metaprint, and A ¹ represents an oxygen atom or a sulfur atom.

a and b are each independently 0 or 1. When a is 0, a carbon atom and a nitrogen atom are bonded by a double bond, and when b is 0, a carbon atom and a nitrogen atom are bonded by a single bond. It is preferable that both a and b are 0. In addition, when both a and b are 0, Formula (10) is expressed as follows.

[Formula 24]

In formula (10), when the moiety represented by Cy in the formula is a cationic moiety, X ¹ represents an anion, and c represents a number necessary to balance the charge. Examples of anions, halide ions (Cl ^-, Br ^-, I ^-), p-toluene sulfonate ion, ethyl sulfate ion, PF ₆ ^-, BF ₄ ^- or ClO ₄ ^-, tris (halo gen alkylsulfonyl) methide anion (e.g. _{(CF 3 SO 2) 3 C} -), di (halo gen alkylsulfonyl) imide anion (e.g. _{(CF 3 SO 2) 2 N} -), tetra cyano anion, the formula a The anion represented by is mentioned. In addition, as the tris(halogenoalkylsulfonyl)methide anion, an anion described in Paragraph No. 0024 of JP 2008-88426 A may be used.

Equation A

[Formula 25]

M ¹ represents a transition metal, n represents an integer of 1 to 2, and R ^A1 to R ^A8 each independently represent a hydrogen atom or a substituent.

Examples of the transition metal include transition metals such as Cu, Co, Ni, Fe, Pd, Pt, Ti, V, Zn, Ru, Rh, and Zr, and Cu, Co, Ni, Fe, Pd and Pt are preferable. , Cu and Ni are more preferable.

As a substituent, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, -OR ²⁰¹ , -COR ²⁰² , -COOR ²⁰³ , -OCOR ²⁰⁴ , -NR ²⁰⁵ R ²⁰⁶ , -NHCOR ²⁰⁷ , -CONR ²⁰⁸ R ²⁰⁹ , -NHCONR ²¹⁰ R ²¹¹ , -NHCOOR ²¹² , -SR ²¹³ , -SO ₂ R ²¹⁴ , -SO ₂ OR ²¹⁵ , -NHSO ₂ R ²¹⁶ or -SO ₂ NR ²¹⁷ R ²¹⁸ is mentioned. Each of R ²⁰¹ to R ²¹⁸ independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. In the case of -COOR ²⁰³ R ²⁰³ is a hydrogen atom (i.e., carboxylic groups), and the hydrogen atoms may be dissociated, or may be a salt state. Further -SO ₂ OR ²¹⁵ R ^215, if the hydrogen atoms (that is, a sulfo group) is dissociated and may be hydrogen atoms, or may be a salt state. The alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, and heteroaryl group include those described for the above substituents, and the preferred ranges are also the same.

For the details of Formula A, reference can be made to the description of paragraphs 0030 to 0050 of JP 2015-40895 A, and this content is intended to be incorporated in the present specification.

In formula (10), when the moiety represented by Cy in the formula is an anion moiety, X ¹ represents a cation, and c represents a number necessary to balance the charge. Examples of cations include alkali metal ions (Li ⁺ , Na ⁺ , K ^+, etc.), alkaline earth metal ions (Mg ²⁺ , Ca ²⁺ , Ba ²⁺ , Sr ^2+, etc.), transition metal ions (Ag ⁺ , Fe ^{2 +} , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^2+, etc.), other metal ions (Al ^3+, etc.), ammonium ions, triethylammonium ions, tributylammonium ions, pyridinium ions, tetrabutyl Ammonium ion, guanidinium ion, tetramethylguanidinium ion, diazabicycloundecenium, etc. are mentioned. As the cation, Na ⁺ , K ⁺ , Mg ²⁺ , Ca ²⁺ , Zn ²⁺ , and diazabicycloundecenium are preferable.

In the formula (10), when the charge at the site represented by Cy in the formula is neutralized in the molecule, X ¹ does not exist. That is, c is 0.

It is also preferable that the compound represented by formula (10) is a compound represented by following (11) or (12). This compound is excellent in heat resistance.

[Formula 26]

In formulas (11) and (12), R ^1A , R ^2A , R ^1B and R ^2B each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group or an aryl group,

L ^1A and L ^1B each independently represent a meta-print consisting of an odd number of meta popular groups,

Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 -or -CR ^X2 R ^X3 -,

R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group,

V ^1A , V ^2A , V ^1B and V ^2B are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, -OR ^c1 , -COR ^c2 , -COOR ^c3 , -OCOR ^c4 , -NR ^c5 R ^c6 , -NHCOR ^c7 , -CONR ^c8 R ^c9 , -NHCONR ^c10 R ^c11 , -NHCOOR ^c12 , -SR ^c13 , -SO ₂ R ^c14 ,- SO ₂ OR ^c15 , -NHSO ₂ R ^c16 or -SO ₂ NR ^c17 R ^c18 is represented, and V ^1A , V ^2A , V ^1B and V ^2B may form a condensed ring,

R ^c1 to R ^c18 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group,

If R is a hydrogen atom ^{c3 c3} of -COOR and -SO ₂ OR a case of ^c15 R ^c15 is a hydrogen atom, and the hydrogen atoms may be dissociated, and even states salt,

m1 and m2 each independently represent 0-4,

When the moiety represented by Cy in the formula is a cation moiety, X ¹ represents an anion, c represents the number necessary to balance the charge,

In the case where the moiety represented by Cy in the formula is an anion moiety, X ¹ represents a cation, c represents the number necessary to balance the charge,

When the charge at the site represented by Cy in the formula is neutralized in the molecule, c is 0.

The groups represented by R ^1A , R ^2A , R ^1B and R ^2B have the same definitions as the alkyl group, alkenyl group, alkynyl group, aralkyl group and aryl group described in R ¹⁰¹ and R ¹⁰² of formula (10), and the preferred range is also the same. These groups may be unsubstituted or have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carboxy group, a sulfo group, an alkoxy group, and an amino group, and a carboxy group and a sulfo group are preferable, and a sulfo group is particularly preferable. The carboxy group and the sulfo group may have a hydrogen atom dissociated or may be in a salt state.

When R ^1A , R ^2A , R ^1B and R ^2B represent an alkyl group, it is more preferably a linear alkyl group.

Y ¹ and Y ² each independently represent -S-, -O-, -NR ^X1 -or -CR ^X2 R ^X3 -, and -NR ^X1 -is preferable.

R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group, and an alkyl group is preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable, and linear is particularly preferable. The alkyl group is particularly preferably a methyl group or an ethyl group.

L ^1A and L ^1B are synonymous with L ^{1 in} formula (10), and their preferred ranges are also the same.

The groups represented by V ^1A , V ^2A , V ^1B and V ^2B are the same as those described for the substituents that the nitrogen-containing heterocycles of Z ¹ and Z ² in Formula (10) may have, and the preferred ranges are also the same.

m1 and m2 each independently represent 0-4, and 0-2 are preferable.

Anions and cations represented by X ¹ is, in the range with the consent described in X ¹ of the formula (10), are also the same preferable range.

The compound represented by formula (10) is preferably a compound represented by the following formulas (10-1) to (10-6).

[Formula 27]

In formulas (10-1) to (10-6), R ^1a and R ^2a each independently represent an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or an aryl group,

X ¹ and X ² each independently represent -S-, -O-, -NR ^X1 -or -CR ^X2 R ^X3 -,

R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or an alkyl group,

R ^3a and R ^4a are each independently a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, an aryl group, a heteroaryl group, -OR ^c1 , -COR ^c2 ,- COOR ^c3 , -OCOR ^c4 , -NR ^c5 R ^c6 , -NHCOR ^c7 , -CONR ^c8 R ^c9 , -NHCONR ^c10 R ^c11 , -NHCOOR ^c12 , -SR ^c13 , -SO ₂ R ^c14 , -SO ₂ OR ^c15 ,- NHSO ₂ R ^c16 , -SO ₂ NR ^c17 R ^c18 or a group represented by the following formula (a),

V ^1a and V ^2a are each independently a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aralkyl group, aryl group, heteroaryl group, -OR ^c1 , -COR ^c2 ,- COOR ^c3 , -OCOR ^c4 , -NR ^c5 R ^c6 , -NHCOR ^c7 , -CONR ^c8 R ^c9 , -NHCONR ^c10 R ^c11 , -NHCOOR ^c12 , -SR ^c13 , -SO ₂ R ^c14 , -SO ₂ OR ^c15 ,- NHSO ₂ R ^c16 or -SO ₂ NR ^c17 R ^c18 ,

V ^1a and V ^2a may form a condensed ring,

R ^c1 to R ^c18 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group,

If R is a hydrogen atom ^{c3 c3} of -COOR and -SO ₂ OR a case of ^c15 R ^c15 is a hydrogen atom, and the hydrogen atoms may be dissociated, and even states salt,

m1 and m2 each independently represent 0-4.

[Formula 28]

In formula (a), * represents a connection part with metaprint, and A ¹ represents an oxygen atom or a sulfur atom.

The groups represented by R ^1a and R ^2a have the same meaning as R ^1A and R ^{1B in} formula (11), and the preferred range is also the same. When R ^1a and R ^2a represent an alkyl group, it is more preferably a linear alkyl group.

X ¹ and X ² have the same definition as Y ¹ and Y ^{2 in} the formula (11), and the preferred ranges are also the same.

R ^3a and R ^4a have the same meaning as the ranges described in the formula (10) and described for the substituents that L ¹ may have, and the preferred ranges are also the same.

The groups represented by V ^1a and V ^2a are the same as the ranges described for the nitrogen-containing heterocycle and the substituents which the ring condensed therein may have, and the preferred ranges are also the same.

m1 and m2 each independently represent 0-4, and 0-2 are preferable.

It is also preferable that the cyanine compound is a compound having an anion represented by the above-described formula A and a cation represented by any one of the following formulas (II-1) to (II-3).

[Chemical Formula 29]

In (II-1) to (II-3), a plurality of D represents independently a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom, and a plurality of R ^a to R ⁱ each independently represent a hydrogen atom Or represents a substituent, R _b and R _c , R _d and R _e , R _e and R _f , R _f and R _g , R _g and R _h and R _h and R _i may be bonded to form a ring, and Z ^a to Z ^c and Y ^a to Y ^d each independently represent a hydrogen atom or a substituent, and Z or Y selected from adjacent two may be bonded to each other to form a ring. As a substituent, the above-mentioned substituent is mentioned.

For details of (II-1) to (II-3), reference may be made to paragraphs 0051 to 0064 of Japanese Unexamined Patent Application Publication No. 2015-40895, the contents of which are incorporated herein by reference.

It is also preferable that the cyanine compound is a compound represented by the following formula (III).

[Formula 30]

In the formula, Q ¹ and Q ² each independently form a nitrogen-containing condensed heterocycle which may have a substituent, and R ¹ and R ² are each independently an alkyl group which may have a substituent or an alkenyl group which may have a substituent Represents, D represents a linking group for forming mono, di, or tricarbocyanine, and X ^- represents a tris(halogenoalkylsulfonyl)methide anion.

As a substituent, the above-mentioned substituent is mentioned. The nitrogen-containing condensed heterocycle represented by Q ¹ and Q ² includes the following formulas (IV-1) to (IV-5).

[Formula 31]

R represents the same meaning as R ¹ and R ² , R ³ represents a halogen atom, an alkyl group, an alkoxy group or a nitro group, and p represents an integer of 0-2. In the case of a nitrogen-containing condensed heterocycle formed by Q ² , it is assumed to be read by changing the structural formula corresponding thereto.

For details of Formula (III), reference can be made to the description of paragraphs 0025 to 0063 of JP 2008-88426 A, and the contents are incorporated herein by reference.

It shows below about a specific example of the compound represented by Formula (10). In addition, in the following table, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, Bn represents a benzyl group, Ph represents a phenyl group, PRS represents C ₃ H ₆ SO ₃ ^- , BUS Represents C ₄ H ₉ SO ₃ ^- . In addition, the numerical value added to the structural formula in the table represents the bonding position of V ¹ and V ² .

In addition, the compound described in paragraph number 0044 to 0045 of JP 2009-108267 A, the compound described in paragraph number 0149 of JP 2014-214262 A, the compound described in paragraph number 0051 to 0068 of JP 2015-40895 A And the compounds described in paragraphs 0047 to 0052 and 0063 of JP 2008-88426 A, the contents of which are incorporated herein by reference.

[Formula 32]

[Table 1]

[Table 2]

[Formula 33]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Formula 34]

[Table 9]

[Table 10]

[Table 11]

[Formula 35]

The coloring composition of the present invention preferably contains 10 to 200 parts by mass, more preferably 20 to 150 parts by mass, and more 30 to 80 parts by mass with respect to 100 parts by mass of the color material that shields the visible light. desirable.

In the colored composition of the present invention, the content of the infrared absorber is preferably 1 to 60% by mass, more preferably 10 to 40% by mass of the total solid content of the colored composition.

In the colored composition of the present invention, the infrared absorber may be used singly or in combination of two or more. When using two or more types together, it is preferable that the total is the said range.

<<Coloring material that blocks light in the visible area>>

Next, a color material that blocks light in the visible region will be described.

In the present invention, it is preferable that the color material that blocks light in the visible region is a material that absorbs light in a wavelength range from purple to red.

Further, in the present invention, it is preferable that the color material that blocks light in the visible region is a color material that blocks light in the wavelength range of 450 to 650 nm.

In the present invention, it is preferable that the color material that blocks light in the visible region satisfies at least one of the following requirements (1) and (2).

(1): Two or more types of chromatic colorants are contained, and black is formed by a combination of two or more types of chromatic colorants.

(2): An organic black colorant is included. In the aspect of (2), it is also preferable to further contain a chromatic colorant.

In addition, in the present invention, the chromatic colorant means a colorant other than a white colorant and a black colorant. The chromatic colorant is preferably a colorant having an absorption maximum in the range of 400 to 700 nm in wavelength. In addition, "having a maximum absorption in the range of a wavelength of 400 to 700 nm" means having a wavelength showing the maximum absorbance in the range of a wavelength of 400 to 700 nm in the absorption spectrum. For example, in the absorption spectrum in the range of 350 to 1300 nm, it is preferable to have a wavelength showing the maximum absorbance in the range of 400 to 700 nm.

In addition, in the present invention, the organic black colorant as a colorant that blocks light in the visible region means a material that absorbs visible light, but transmits at least part of infrared rays. Accordingly, in the present invention, the organic black colorant as a colorant that blocks light in the visible region does not contain a black colorant that absorbs both visible and infrared light, such as carbon black or titanium black.

In the present invention, the colorant for blocking light in the visible region is, for example, A/ which is the ratio of the minimum value A of absorbance in the range of 450 to 650 nm and the minimum value B of absorbance in the range of 900 to 1300 nm. It is preferable that B is 4.5 or more.

The above characteristics may be satisfied by one type of material, or may be satisfied by a combination of a plurality of materials. For example, in the case of the aspect (1), it is preferable that a plurality of chromatic colorants are combined to satisfy the spectral characteristics. Moreover, in the case of the aspect of the above (2), the organic black colorant may satisfy the spectral characteristics. Further, the above spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.

(Chromic colorant)

In the present invention, the chromatic colorant is preferably a colorant selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant and an orange colorant.

In the present invention, the chromatic colorant may be a pigment or a dye. It is preferably a pigment.

The pigment preferably has an average particle diameter (r) of 20 nm≦r≦300 nm, more preferably 25 nm≦r≦250 nm, and particularly preferably 30 nm≦r≦200 nm. The "average particle diameter" as used herein refers to the average particle diameter of the secondary particles collected by the primary particles of the pigment.

In addition, the particle size distribution of the secondary particles of the pigment that can be used (hereinafter, also simply referred to as “particle size distribution”) is that the secondary particles entering (average particle diameter ± 100) nm are not less than 70% by mass of the total, preferably 80 It is preferably not less than mass%. In addition, the particle size distribution of the secondary particles can be measured using a scattering intensity distribution.

The pigment having the secondary particle diameter and the particle diameter distribution of the secondary particles described above is a commercially available pigment, together with other pigments used in some cases (the average particle diameter of the secondary particles is usually more than 300 nm), preferably a resin. And a pigment mixture mixed with an organic solvent, for example, using a grinder such as a bead mill or a roll mill, and mixing and dispersing while grinding. The pigment obtained in this way usually takes the form of a pigment dispersion.

It is preferable that a pigment is an organic pigment, and the following things are mentioned. However, this invention is not limited to these.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35 :1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94 , 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137 , 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176 , 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc. (over, yellow pigment),

CI Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 Etc (above, orange pigment),

CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4 , 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3 , 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279, etc. Red pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (over, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, etc. (over, purple pigment),

C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (more, blue pigment),

These organic pigments can be used alone or in various combinations.

There is no restriction|limiting in particular as a dye, A well-known dye can be used. As a chemical structure, pyrazole azo system, anilino azo system, triarylmethane system, anthraquinone system, anthrapyridone system, benzylidene system, oxonol system, pyrazolo triazole azo system, pyridone azo system, cyanine system, phenothiazine Dyes such as pyrrolopyrazole azomethine-based, xanthene-based, phthalocyanine-based, benzopyran-based, indigo-based, and pyromethene-based dye can be used. Moreover, you may use a multimer of these dyes. In addition, the dyes described in JP 2015-028144 A and JP 2015-34966 A can also be used.

Moreover, as a dye, an acidic dye and/or its derivative may be used suitably in some cases.

In addition, direct dyes, basic dyes, mordant dyes, acidic mordant dyes, azoic dyes, disperse dyes, oil dyes, food dyes, and/or derivatives thereof can also be usefully used.

Although specific examples of the acidic dye are given below, it is not limited to these. For example, the following dyes and derivatives of these dyes are mentioned.

acid alizarin violet N,

acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40~45, 62, 70, 74, 80, 83, 86, 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324:1,

acid chrome violet K,

acid Fuchsin; acid green 1, 3, 5, 9, 16, 25, 27, 50,

acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95,

acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274,

acid violet 6B, 7, 9, 17, 19,

acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243,

Food Yellow 3

In addition, an azo-based, xanthene-based, or phthalocyanine-based acid dye other than the above is also preferable, and C. I. Solvent Blue 44, 38; C. I. Solvent orange 45; Acid dyes such as Rhodamine B and Rhodamine 110, and derivatives of these dyes are also preferably used.

Among them, as a dye, triarylmethane-based, anthraquinone-based, azomethine-based, benzylidene-based, oxonol-based, cyanine-based, phenothiazine-based, pyrrolopyrazole azomethane-based, xanthene-based, phthalocyanine It is preferable that it is at least 1 type selected from the system, benzopyran system, indigo system, pyrazole azo system, anilino azo system, pyrazolo triazole azo system, a pyridone azo system, an anthrapyridone system, and a pyromethene system.

Further, you may use a combination of a pigment and a dye.

When a chromatic colorant is formed black by a combination of two or more chromatic colorants, examples of the combination of the chromatic colorant include the following.

(1) An aspect containing a yellow colorant, a blue colorant, a purple colorant and a red colorant.

(2) An aspect containing a yellow colorant, a blue colorant and a red colorant.

(3) An aspect containing a yellow colorant, a purple colorant and a red colorant.

(4) An aspect containing a yellow colorant and a purple colorant.

(5) An aspect containing a green colorant, a blue colorant, a purple colorant and a red colorant.

(6) An aspect containing a purple colorant and an orange colorant.

(7) An aspect containing a green colorant, a purple colorant and a red colorant.

(8) An aspect containing a green colorant and a red colorant.

Specific examples of the aspect of the above (1) include CI Pigment Yellow 139 or 185 as a yellow pigment, CI Pigment Blue 15:6 as a blue pigment, CI Pigment Violet 23 as a purple pigment, and CI Pigment Red 254 or 224 as a red pigment. The aspect containing it is mentioned.

As a specific example of the aspect of said (2), the aspect containing C. I. Pigment Yellow 139 or 185 as a yellow pigment, C. I. Pigment Blue 15:6 as a blue pigment, and C. I. Pigment Red 254 or 224 as a red pigment can be mentioned.

As a specific example of the aspect of said (3), the aspect containing C. I. Pigment Yellow 139 or 185 as a yellow pigment, C. I. Pigment Violet 23 as a purple pigment, and C. I. Pigment Red 254 or 224 as a red pigment can be mentioned.

As a specific example of the aspect of said (4), the aspect containing C. I. Pigment Yellow 139 or 185 as a yellow pigment, and C. I. Pigment Violet 23 as a purple pigment is mentioned.

Specific examples of the aspect of the above (5) include CI Pigment Green 7 or 36 as a green pigment, CI Pigment Blue 15:6 as a blue pigment, CI Pigment Violet 23 as a purple pigment, and CI Pigment Red 254 or 224 as a red pigment. The aspect containing it is mentioned.

As a specific example of the aspect of said (6), the aspect containing C. I. Pigment Violet 23 as a purple pigment and C. I. Pigment Orange 71 as an orange pigment is mentioned.

Specific examples of the above (7) include C. I. Pigment Green 7 or 36 as a green pigment, C. I. Pigment Violet 23 as a purple pigment, and C. I. Pigment Red 254 or 224 as a red pigment.

As a specific example of said (8), the aspect containing C. I. Pigment Green 7 or 36 as a green pigment, and C. I. Pigment Red 254 or 224 as a red pigment is mentioned.

Examples of the proportion (mass ratio) of each colorant include the following.

[Table 12]

(Organic black colorant)

In the present invention, examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.

Examples of the bisbenzofuranone compound include those described in JP 2010-534726 A, JP 2012-515233 A, JP 2012-515234 A, etc., for example, "Irgaphor Black" manufactured by BASF. It is available as.

As a perylene compound, C. I. Pigment Black 31, 32, etc. are mentioned.

Examples of the azomethine compound include those described in Japanese Unexamined Patent Application Publication No. Hei1-170601, Japanese Unexamined Patent Application Publication No. 2-34664, etc., for example, available as "chromofine black A1103" manufactured by Dainichi Seika. I can.

Although the azo compound is not specifically limited, The compound etc. which are represented by following formula (A-1) are mentioned suitably.

[Formula 36]

In the present invention, the bisbenzofuranone compound is preferably a compound represented by the following formula and a mixture thereof.

[Formula 37]

In the formula, R ¹ and R ² each independently represent a hydrogen atom or a substituent,

R ³ and R ⁴ each independently represent a substituent, a and b each independently represent an integer of 0 to 4, and when a is 2 or more, a plurality of R ³ may be the same or different, and a plurality of R ³ may be bonded to form a ring, and when b is 2 or more, a plurality of R ⁴ may be the same or different, and a plurality of R ⁴ may be bonded to form a ring.

Substituents represented by R ¹ to R ⁴ are halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkyneyl group, aralkyl group, aryl group, heteroaryl group, -OR ³⁰¹ , -COR ³⁰² ,- COOR ³⁰³ , -OCOR ³⁰⁴ , -NR ³⁰⁵ R ³⁰⁶ , -NHCOR ³⁰⁷ , -CONR ³⁰⁸ R ³⁰⁹ , -NHCONR ³¹⁰ R ³¹¹ , -NHCOOR ³¹² , -SR ³¹³ , -SO ₂ R ³¹⁴ , -SO ₂ OR ³¹⁵ ,- NHSO ₂ R ³¹⁶ or -SO ₂ NR ³¹⁷ R ³¹⁸ is represented, and R ³⁰¹ to R ³¹⁸ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heteroaryl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The number of carbon atoms of the alkyl group is preferably 1 to 12. The alkyl group may be linear, branched or cyclic.

The number of carbon atoms of the alkenyl group is preferably 2 to 12. The alkenyl group may be linear, branched or cyclic.

The number of carbon atoms of the alkyneyl group is preferably 2 to 12. The alkyneyl group may be either linear or branched.

The aryl group preferably has 6 to 12 carbon atoms.

The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched or cyclic.

As for the carbon number of an alkenyl group, 2-20 are preferable, 2-12 are more preferable, and 2-8 are especially preferable. The alkenyl group may be linear, branched or cyclic.

The number of carbon atoms of the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkyneyl group may be either linear or branched.

The number of carbon atoms of the aryl group is preferably 6 to 25, more preferably 6 to 15, and most preferably 6 to 12.

The alkyl moiety of the aralkyl group is the same as the alkyl group. The aryl moiety of the aralkyl group is the same as the aryl group. The number of carbon atoms of the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and still more preferably 7 to 25.

The heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring having 2 to 8 condensation numbers, and more preferably a monocyclic ring or a condensed ring having 2 to 4 condensation numbers. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The hetero atom constituting the ring of the heteroaryl group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. The heteroaryl group is preferably a 5- or 6-membered ring. The heteroaryl group is preferably a 5- or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12.

For details of the bisbenzofuranone compound, reference can be made to the description of paragraphs 0014 to 0037 of Japanese Laid-Open Patent Publication No. 2010-534726, and the contents are incorporated herein by reference.

In the present invention, when an organic black colorant is used as a colorant that blocks light in the visible region, it is preferably used in combination with a chromatic colorant. By using an organic black colorant and a chromatic colorant together, it is easy to obtain excellent spectral characteristics. Examples of the chromatic colorant used in combination with an organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used independently and may use 2 or more types together.

Moreover, as for the mixing ratio of a chromatic colorant and an organic black colorant, 10 to 200 mass parts of a chromatic colorant are preferable, and 15 to 150 mass parts are more preferable with respect to 100 mass parts of an organic black colorant.

In the present invention, in the colorant for blocking visible light, the content of the pigment is preferably 95% by mass or more, and more preferably 97% by mass or more with respect to the total amount of the colorant for blocking visible light, It is more preferably 99% by mass or more.

In the colored composition of the present invention, the content of the colorant that blocks light in the visible region is preferably 10 to 60% by mass, and more preferably 30 to 50% by mass of the total solid content of the colored composition.

In the coloring composition of the present invention, the total amount of the infrared absorber and the colorant for blocking light in the visible region is preferably 1 to 80% by mass, more preferably 20 to 70% by mass, based on the total solid content of the colored composition. And it is more preferably 30 to 70% by mass.

As for the spectral characteristics of the colored composition of the present invention, it is preferable that A/B, which is the ratio of the minimum value A of absorbance in the range of wavelength 400 to 830 nm and the maximum value B of absorbance in the range of wavelength 1000 to 1300 nm, is 4.5 or more. Do. As for A/B mentioned above, 10 or more are preferable, 15 or more are more preferable, and 30 or more are still more preferable.

When the ratio of the absorbance is 4.5 or more, the maximum value of the transmittance of light in the thickness direction of the film in the range of 400 to 830 nm is 20% or less, and the transmittance of the light in the thickness direction of the film is in the range of 1000 to 1300 nm A film having a spectral characteristic having a minimum value of 70% or more can be suitably formed.

The absorbance Aλ at a certain wavelength λ is defined by the following equation (1).

Aλ=-log(Tλ)...(1)

Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance at the wavelength λ.

In the present invention, the value of absorbance may be a value measured in a solution state, or may be a value in a film formed by using a colored composition. In the case of measuring the absorbance in the film state, a colored composition is coated on a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined film thickness, and dried on a hot plate at 100°C for 120 seconds to prepare It is preferred to use a membrane. The film thickness of the film can be measured using a stylus type surface shape measuring device (DEKTAK150 manufactured by ULVAC) on a substrate having a film.

Moreover, the absorbance can be measured using a conventionally known spectrophotometer. The measurement conditions for absorbance are not particularly limited, but the maximum value B of the absorbance in the range of 1000 to 1300 nm is measured under the condition that the minimum value A of the absorbance in the range of 400 to 830 nm is adjusted to be 0.1 to 3.0. It is desirable to do. By measuring the absorbance under such conditions, the measurement error can be made smaller. There is no restriction|limiting in particular as a method of adjusting so that the minimum value A of absorbance in a wavelength range of 400-830 nm becomes 0.1-3.0. For example, when measuring the absorbance in the state of a colored composition, a method of adjusting the optical path length of the sample cell is exemplified. Moreover, when measuring the absorbance in a film state, a method of adjusting the film thickness, etc. are mentioned.

Measurement methods, such as spectral properties and film thickness, of the film formed by the colored composition of the present invention are shown below.

The colored composition of the present invention was applied onto a glass substrate by a method such as spin coating so that the film thickness after drying became the predetermined film thickness described above, and dried on a hot plate at 100° C. for 120 seconds.

The film thickness of the film was measured using a stylus type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC) on the dried substrate having the film.

The dried substrate having this film was measured for transmittance in a range of 300 to 1300 nm in wavelength using an ultraviolet visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High Technologies).

<<<resin>>>

The coloring composition of this invention can contain resin. The resin is blended, for example, for use in dispersing a pigment in the composition or for use as a binder. In addition, resins mainly used to disperse pigments and the like are also referred to as dispersants. However, such a use of a resin is an example, and it can also be used for purposes other than such a use.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. 1,000,000 or less are preferable and, as for the upper limit, 500,000 or less are more preferable. As for the lower limit, 3,000 or more are preferable and 5,000 or more are more preferable.

The content of the resin is preferably 10 to 80% by mass, and more preferably 20 to 60% by mass of the total solid content of the colored composition. The coloring composition may contain only one type of resin, and may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

(Dispersant)

The colored composition of the present invention may contain a dispersant as a resin.

Examples of the dispersant include polymeric dispersants (for example, resins having an amine group (polyamideamine and salts thereof), oligoimine resins, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethane, modified polyester, Modified poly(meth)acrylate, (meth)acrylic copolymer, naphthalene sulfonic acid formalin condensate], and the like.

Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from their structure.

Further, as the polymer dispersant, a resin having an acid value of 60 mgKOH/g or more (more preferably, an acid value of 60 mgKOH/g or more and 300 mgKOH/g or less) is also preferably mentioned.

As the terminal-modified polymer, for example, a polymer having a phosphoric acid group at the terminal described in Japanese Unexamined Patent Publication No. Hei 3-112992, Japanese Unexamined Patent Publication No. 2003-533455, etc., and a sulfonic acid group at the terminal described in JP 2002-273191 A. And polymers having a partial skeleton or heterocycle of organic dyes described in Japanese Patent Application Laid-Open No. Hei 9-77994 and the like. In addition, polymers in which anchor sites (acid groups, basic groups, partial skeletons of organic dyes, heterocycles, etc.) to the surface of two or more pigments are introduced at the end of the polymer described in Japanese Patent Application Laid-Open No. 2007-277514 are also preferable because of their excellent dispersion stability. Do.

As a graft-type polymer, for example, the reaction product of poly(lower alkyleneimine) and polyester described in JP-A-54-37082A, JP-A-8-507960A, JP-A2009-258668, etc. , The reaction product of polyallylamine and polyester described in Japanese Unexamined Patent Application Publication No. Hei 9-169821, etc., and the macromonomer and nitrogen atom-containing group described in Japanese Unexamined Patent Publication No. Hei 10-339949 and 2004-37986 A copolymer of monomers, a graft-type polymer having a partial skeleton or a heterocycle of an organic dye described in JP 2003-238837 A, JP 2008-9426 A, JP 2008-81732 A, etc. A copolymer of a macromonomer and an acid group-containing monomer described in Publication No. 2010-106268 or the like may be mentioned.

As a macromonomer used when producing a graft-type polymer by radical polymerization, a known macromonomer can be used, and macromonomer AA-6 manufactured by Toa Kosei Co., Ltd. (polymethyl methacrylate whose terminal group is a methacryloyl group) , AS-6 (polystyrene terminal group methacryloyl group), AN-6S (copolymer of styrene and acrylonitrile terminal group methacryloyl group), AB-6 (polystyrene terminal group methacryloyl group) Butyl acrylate), Flaxel FM5 manufactured by Daicel Co., Ltd. (5 mole equivalent of ε-caprolactone of 2-hydroxyethyl methacrylate), FA10L (10 mole equivalent of ε-caprolactone of 2-hydroxyethyl acrylate) Additives), and the polyester-based macromonomer described in Japanese Laid-Open Patent Publication No. Hei 2-272009. Among these, polyester-based macromonomers having excellent flexibility and hydrophilic properties are particularly preferred from the viewpoint of dispersibility of the pigment dispersion, dispersion stability, and developability exhibited by the coloring composition using the pigment dispersion. The polyester macromonomer represented by the polyester macromonomer described in Hei 2-272009 is most preferred.

As the block-type polymer, the block-type polymer described in Japanese Unexamined Patent Application Publication No. 2003-49110, Japanese Unexamined Patent Application Publication No. 2009-52010, etc. is preferable.

The resin can also use a graft copolymer containing a structural unit represented by any one of the following formulas (1) to (4).

[Formula 38]

X ¹ , X ² , X ³ , X ⁴ , and X ⁵ each independently represent a hydrogen atom or a monovalent organic group. A hydrogen atom or an alkyl group having 1 to 12 carbon atoms is preferable, a hydrogen atom or a methyl group is more preferable, and a methyl group is particularly preferable.

W ¹ , W ² , W ³ , and W ⁴ each independently represent an oxygen atom or NH, and an oxygen atom is preferred.

R ³ represents a branched or straight chain alkylene group (the number of carbons is preferably 1 to 10, and more preferably 2 or 3), and from the viewpoint of dispersion stability, represented by -CH ₂ -CH (CH ₃ )- A group or a group represented by -CH(CH ₃ )-CH ₂ -is preferable.

Y ¹ , Y ² , Y ³ , and Y ⁴ are each independently a divalent linking group, and are not particularly limited in terms of structure.

For the graft copolymer, reference may be made to the description of paragraphs 0025 to 0069 of JP 2012-255128 A, and the above contents are incorporated herein by reference.

As a specific example of the said graft copolymer, the following is mentioned, for example. Moreover, the resin described in paragraphs 0072 to 0094 of JP 2012-255128 A can be used.

[Formula 39]

Moreover, the resin can also use an oligoimine type dispersant containing a nitrogen atom in at least one of the main chain and the side chain. As an oligoimine-based dispersant, a resin having a structural unit having a partial structure X having a functional group of pKa14 or less, a side chain containing a side chain Y having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain Is preferred. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom showing basicity.

The oligoimine-based dispersant includes, for example, a structural unit represented by the following formula (I-1), a structural unit represented by the formula (I-2), and/or a structural unit represented by the formula (I-2a). And the like.

[Formula 40]

Each of R ¹ and R ² independently represents a hydrogen atom, a halogen atom, or an alkyl group (preferably having 1 to 6 carbon atoms). a represents the integer of 1-5 each independently. * Indicates the connection between structural units.

R ⁸ and R ⁹ are groups synonymous with R ¹ .

L is a single bond, an alkylene group (preferably having 1 to 6 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), an arylene group (preferably having 6 to 24 carbon atoms), and a heteroarylene group (with 1 to 6 carbon atoms being preferred). Is preferable), an imino group (preferably having 0 to 6 carbon atoms), an ether group, a thioether group, a carbonyl group, or a linking group related to a combination thereof. Especially, it is preferable that it is a single bond or -CR ⁵ R ⁶ -NR ^7- (the imino group becomes X or Y side). Here, R ⁵ R ⁶ each independently represents a hydrogen atom, a halogen atom, and an alkyl group (preferably having 1 to 6 carbon atoms). R ⁷ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

L ^a is a structural moiety forming a ring structure together with CR ⁸ CR ⁹ and N, and is preferably a structural moiety forming a non-aromatic heterocycle having 3 to 7 carbon atoms in combination with the carbon atoms of CR ⁸ CR ⁹ . More preferably, it is a structural moiety that forms a 5- to 7-membered non-aromatic heterocycle by combining the carbon atom and N (nitrogen atom) of CR ⁸ CR ⁹ , more preferably forming a 5-membered non-aromatic heterocycle. It is a structural part, and it is especially preferable that it is a structural part which forms pyrrolidine. This structural moiety may further have a substituent such as an alkyl group.

X represents a group having a functional group of pKa14 or less.

Y represents a side chain of 40-10,000 atoms.

The dispersant (oligoimine dispersant) may further contain one or more types selected from structural units represented by formulas (I-3), (I-4), and (I-5) as a copolymerization component. When the dispersant contains such a structural unit, the dispersing performance can be further improved.

[Formula 41]

R ¹ , R ² , R ⁸ , R ⁹ , L, La, a and * are the definitions and agreements in formulas (I-1), (I-2), and (I-2a).

Ya represents a side chain of 40-10,000 atoms having an anionic group. The structural unit represented by formula (I-3) can be formed by adding and reacting an oligomer or polymer having a group reacting with an amine to form a salt to a resin having a primary or secondary amino group in the main chain portion.

For the oligoimine-based dispersant, reference can be made to the description of paragraphs 0102 to 0166 of JP 2012-255128 A, and the above contents are incorporated herein by reference.

As a specific example of an oligoimine type dispersant, the following can be mentioned, for example. Moreover, the resin described in paragraphs 0168 to 0174 of JP 2012-255128 A can be used.

[Formula 42]

The resin can also use a resin containing a structural unit represented by the following formula (P1). By using the following resin, the dispersibility of the infrared absorber (particularly, the pyrrolopyrrole dye compound represented by formula (1)) can be further improved.

[Formula 43]

In formula (P1), R ¹ represents hydrogen or a methyl group, R ² represents an alkylene group, and Z represents a nitrogen-containing heterocyclic structure.

Although it does not specifically limit as an alkylene group represented by R ² , For example, methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, 2-hydroxypropylene group, methyleneoxy group, ethyleneoxy group, methylene An oxycarbonyl group, a methylenethio group, etc. are mentioned suitably, and a methylene group, a methyleneoxy group, a methyleneoxycarbonyl group, and a methylenethio group are more preferable.

The nitrogen-containing heterocyclic structure represented by Z is, for example, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a quinoline ring, an acridine ring, and a phenothia. What has a true ring, a phenoxazine ring, an acridon ring, an anthraquinone ring, a benzimidazole structure, a benzotriazole structure, a benzothiazole structure, a cyclic amide structure, a cyclic urea structure, and a cyclic imide structure. Among these, as the nitrogen-containing heterocyclic structure represented by Z, a structure represented by the following formula (P2) or (P3) is preferable.

[Formula 44]

In formula (P2), X is a single bond, an alkylene group (e.g., methylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, etc.), -O-, -S-, -NR-, and- It is any one selected from the group consisting of C(=O)-. In addition, here, R represents a hydrogen atom or an alkyl group, and examples of the alkyl group when R represents an alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, n -Hexyl group, n-octyl group, 2-ethylhexyl group, n-octadecyl group, etc. are mentioned.

Among these, X is preferably a single bond, a methylene group, -O-, and -C(=O)-, and particularly preferably -C(=O)-.

In formulas (P2) and (P3), ring A, ring B, and ring C each independently represent an aromatic ring. As an aromatic ring, for example, a benzene ring, a naphthalene ring, an indene ring, an azulene ring, a fluorene ring, an anthracene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyrrole ring, an imidazole ring, an indole ring, a quinoline ring, a Cridine ring, phenothiazine ring, phenoxazine ring, acridon ring, anthraquinone ring, etc. are mentioned, Among them, a benzene ring, a naphthalene ring, an anthracene ring, a pyridine ring, a phenoxazine ring, an acridine ring, a phenothione An azine ring, a phenoxazine ring, an acridon ring, and an anthraquinone ring are preferable, and a benzene ring, a naphthalene ring, and a pyridine ring are particularly preferable.

As a specific example of the structural unit represented by Formula (P1), the following is mentioned, for example. In addition, reference may be made to the description of paragraph number 0023 of JP 2008-009426 A, and this content is assumed to be incorporated herein.

[Formula 45]

The resin containing the structural unit represented by formula (P1) may further contain a structural unit represented by any one of formulas (1) to (4) of the resin described above. In addition, any one of formulas (I-1), formula (I-2), formula (I-2a), formula (I-3), formula (I-4), and formula (I-5) of the above resin The structural unit to appear may further be included.

The following is mentioned as a specific example of the resin containing the structural unit represented by Formula (P1).

[Chemical Formula 46]

Resins are also commercially available, and as such specific examples, BYK Chemie's "Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide) ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)", "EFKA4047, 4050~4165 (polyuretaine-based)" manufactured by EFKA ), EFKA4330~4340 (block copolymer), 4400~4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivative), 6750 (azo pigment derivative)", "Azisper-PB821, PB822, PB880, PB881" manufactured by Ajinomoto Fine Techno, "Florene TG-710 (Uretain Oligomer)" manufactured by Kyoeisha Chemicals , "Polyflo No. 50E, No. 300 (acrylic copolymer)", "Disparon KS-860, 873SN, 874, #2150 (aliphatic polyhydric carboxylic acid), #7004 (polyether ester)" manufactured by Kusumoto Kasei ), DA-703-50, DA-705, DA-725", "Demol RN, N (naphthalene sulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate) manufactured by Gao Corporation ", "Homogenol L-18 (polymer polycarboxylic acid)", "Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "Acetamine 86 (stearylamine acetate)", Nippon Lu "Solspurs 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, manufactured by Brisol Co., Ltd. 32000, 38500 (Graft-type polymer)", "Nikko Chemicals T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)", Kawaken Fine Chemicals " Hinoact T-8000E", "Organosiloxane Polymer KP-341" manufactured by Shin-Etsu Chemical Co., Ltd., "EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100" manufactured by Morishita Sangyo Corporation, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450", "Disperse Ade 6, Disperse Ade 8, Disperse Ade 15, Disperse Ade 9100" manufactured by Sannovco, Inc. "Adeka" manufactured by ADEKA Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123, and Sanyo Kasei Co., Ltd. Eonet S-20" and the like.

These resins may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative described later and a polymer dispersant. Further, the resin may be used in combination with an alkali-soluble resin described later together with a terminal modified polymer having an anchor site on the pigment surface, a graft polymer, and a block polymer. Examples of the alkali-soluble resin include (meth)acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc., acidic cellulose derivatives having a carboxylic acid in the side chain, and polymers having hydroxyl groups. A resin modified with an acid anhydride is mentioned, but a (meth)acrylic acid copolymer is particularly preferred. In addition, the N-position substituted maleimide monomer copolymer described in Japanese Unexamined Patent Application Publication No. Hei 10-300922, the ether dimer copolymer described in Japanese Unexamined Patent Application Publication No. 2004-300204, and the polymerizable group described in Japanese Unexamined Patent Application Publication No. Hei 7-319161 The alkali-soluble resin to contain is also preferable.

The content of the dispersant is preferably 1 to 80 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 10 to 60 parts by mass with respect to 100 parts by mass of the pigment.

(Alkaline Soluble Resin)

It is preferable that the coloring composition of this invention contains an alkali-soluble resin as resin. By containing an alkali-soluble resin, developability and pattern formation property are improved. Moreover, alkali-soluble resin can also be used as a dispersing agent or a binder.

Although it does not specifically set as a molecular weight of an alkali-soluble resin, It is preferable that the weight average molecular weight (Mw) is 5000-100,000. Moreover, it is preferable that the number average molecular weight (Mn) is 1000-20,000.

As the alkali-soluble resin, a linear organic polymer may be used, and it can be appropriately selected from resins having at least one group promoting alkali dissolution in a molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as a main chain).

As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxy styrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic/acrylamide copolymer resin are preferable, and from the viewpoint of developability control, acrylic resin , Acrylamide resin, and acrylic/acrylamide copolymer resin are preferable.

As a group that promotes alkali dissolution (hereinafter, also referred to as an acid group), for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxy group, or the like is preferable. These acid groups may be only one type or two or more types.

For the production of an alkali-soluble resin, for example, a known radical polymerization method can be applied. When preparing an alkali-soluble resin by the radical polymerization method, polymerization conditions such as temperature, pressure, type and amount of radical initiator, and type of solvent can be easily set by a person skilled in the art, and conditions can be determined experimentally. .

As the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer, and a novolac Alkali-soluble phenolic resins such as type resin, acidic cellulose derivatives having a carboxy group in the side chain, and resins obtained by adding an acid anhydride to a polymer having a hydroxy group may be mentioned. In particular, a copolymer of (meth)acrylic acid and another monomer copolymerizable therewith is suitable as an alkali-soluble resin. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylate, aryl (meth)acrylate, vinyl compounds, and the like. As alkyl (meth)acrylate and aryl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate , Pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, tolyl (meth)acrylate, naphthyl (meth)acrylate As a vinyl compound, such as cyclohexyl (meth)acrylate, styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinylacetate, N-vinylpyrrolidone, tetrahydro Furfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. As another monomer, an N-position substituted maleimide monomer described in Japanese Laid-Open Patent Publication No. Hei 10-300922, for example, N-phenylmaleimide, N-cyclohexylmaleimide, or the like may be used. Moreover, only 1 type may be sufficient as these (meth)acrylic acid and other monomer copolymerizable, and 2 or more types may be sufficient as it.

Further, in order to improve the crosslinking efficiency of the film, an alkali-soluble resin having a polymerizable group may be used. As a polymerizable group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin or the like containing a polymerizable group in the side chain is useful.

Examples of the alkali-soluble resin containing a polymerizable group include Diamond NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer6173 (COOH-containing polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co., Ltd.), Viscoat R-264, and KS resist 106 106 (All made by Osaka Yuki Chemical High School Co., Ltd.), Cyclomer P series (e.g. ACA230AA), Flaxel CF200 series (all made by Daicel), Ebecryl3800 (made by Daicel Yushibi Co., Ltd.), Acliqueure RD-F8 (made by Nippon Shokubai), etc. are mentioned.

The alkali-soluble resin is a benzyl (meth)acrylate/(meth)acrylic acid copolymer, a benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate copolymer, and a benzyl (meth)acrylate. A multipolymer composed of /(meth)acrylic acid/other monomers can be preferably used. In addition, a copolymer of 2-hydroxyethyl (meth)acrylate, described in Japanese Patent Laid-Open No. Hei 7-140654, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacryl Acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate/polymethylmethacrylate macromonomer/benzylmethacrylate/methacrylic acid copolymer, 2-hydroxyethylmethacrylate/polystyrene macromonomer/methyl Methacrylate/methacrylic acid copolymer, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymer, and the like can also be preferably used.

Moreover, as a commercial item, FF-426 (made by Fujikura Kasei Co., Ltd.) etc. can also be used, for example.

Alkali-soluble resin is a polymer formed by polymerizing a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds are sometimes referred to as "ether dimers") It is also preferable to include.

[Chemical Formula 47]

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[Formula 48]

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of formula (ED2), description of Japanese Laid-Open Patent Publication No. 2010-168539 can be referred to.

In formula (ED1), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, but, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl , Isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl, and other linear or branched alkyl groups; Aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; An alkyl group substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; An alkyl group substituted with an aryl group such as benzyl; And the like. Among these, a substituent of primary or secondary carbon that is difficult to desorb by acid or heat, such as methyl, ethyl, cyclohexyl, benzyl, and the like, is particularly preferable from the viewpoint of heat resistance.

As a specific example of the ether dimer, the description of paragraph No. 0317 of JP 2013-29760 A can be referred, for example, and this content is assumed to be incorporated herein. There may be only one type of ether dimer, and may be two or more types.

The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

[Chemical Formula 49]

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents an alkyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring. Represents. n represents the integer of 1-15.

In the formula (X), the number of carbon atoms of the alkylene group of R ₂ is preferably 2 to 3. Moreover, although carbon number of the alkyl group of R ₃ is 1-20, More preferably, it is 1-10, and the alkyl group of R ₃ may contain a benzene ring. Examples of the alkyl group containing the benzene ring represented by R ₃ include a benzyl group and a 2-phenyl (iso)propyl group.

As a specific example of an alkali-soluble resin, the following is mentioned.

[Formula 50]

[Chemical Formula 51]

For the alkali-soluble resin, reference can be made to the description of paragraphs 0558 to 0571 of JP 2012-208494 A (corresponding U.S. Patent Application Publication No. 2012/0235099 0685 to 0700), the contents of which are incorporated herein by reference. It should be done.

In addition, the copolymer (B) described in paragraphs 0029 to 0063 of JP 2012-32767 A and the alkali-soluble resin used in the examples, the binder resin described in paragraphs 0088 to 0098 of JP 2012-208474, and The binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP 2012-137531 A, and the binder resin used in the examples, paragraphs 0132 to 0143 of JP 2013-024934 A. The described binder resin and the binder resin used in the examples, the binder resin described in paragraphs 0092 to 0098 of JP 2011-242752 A and the binder resin used in the examples, paragraph number of JP 2012-032770 A The binder resin described in 0030 to 072 can also be used. These contents are assumed to be incorporated in this specification.

The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and still more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and even more preferably 120 mgKOH/g or less.

The content of the alkali-soluble resin is preferably 0.1 to 20% by mass with respect to the total solid content of the colored composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is more preferably 12% by mass or less, and still more preferably 10% by mass or less. The coloring composition of this invention may contain only one type, and may contain two or more types of alkali-soluble resin. When it contains two or more types, it is preferable that the total amount becomes the said range.

<<<pigment derivative>>>

The coloring composition of the present invention may contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, or a phthalimide methyl group. The pigment derivative preferably contains a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.

As organic pigments for constituting the pigment derivatives, pyrrolopyrrole pigments, diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylenes Pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, indanthrene pigments, metal complex pigments, and the like.

Moreover, as the acidic group which the pigment derivative has, a sulfonic acid, a carboxylic acid, and its quaternary ammonium salt are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is particularly preferable. As the basic group which the pigment derivative has, an amino group is preferable, and a tertiary amino group is particularly preferable.

As the pigment derivative, a pyrrolopyrrole pigment derivative, a quinoline pigment derivative, a benzimidazolone pigment derivative, and an isoindolin pigment derivative are preferred, and a pyrrolopyrrole pigment derivative is particularly preferred.

The following are mentioned as a specific example of a pigment derivative.

[Formula 52]

The content of the pigment derivative is preferably 1 to 50% by mass, and more preferably 3 to 30% by mass with respect to the total mass of the pigment. As for the pigment derivative, only 1 type may be used and 2 or more types may be used together.

<<<polymerizable compound>>>

It is preferable that the coloring composition of this invention contains a polymeric compound. As the polymerizable compound, a known compound capable of crosslinking by radical, acid or heat can be used. For example, a compound having a group having an ethylenically unsaturated bond, a methylol group, or the like can be mentioned. Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. In the present invention, the polymerizable compound is more preferably a radical polymerizable compound.

In the present invention, the polymerizable compound may be any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and multimers thereof. Monomers are preferred.

The molecular weight of the polymerizable compound is preferably 100 to 3000. 2000 or less are preferable and, as for the upper limit, 1500 or less are more preferable. 150 or more are preferable and, as for a lower limit, 250 or more are more preferable.

It is preferable that it is a 3-15 functional (meth)acrylate compound, and, as for a polymeric compound, it is more preferable that it is a 3-6 functional (meth)acrylate compound.

Examples of the monomer and prepolymer include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof, Preferably, they are esters of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and amides of an unsaturated carboxylic acid and an aliphatic polyhydric amine compound, and a multimer thereof. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxy group, an amino group, or a mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, or a monofunctional or polyfunctional carboxylic acid Dehydration and condensation reactants with and the like are also suitably used. In addition, the reaction product of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group, monofunctional or polyfunctional alcohols, amines, thiols, halogen atom or tosyloxy group, etc. Reaction products of unsaturated carboxylic acid esters or amides having a sexual substituent and monofunctional or polyfunctional alcohols, amines, and thiols are also suitable. In place of the above unsaturated carboxylic acid, it is also possible to use a group of compounds substituted with vinylbenzene derivatives such as unsaturated phosphonic acid and styrene, vinyl ether and allyl ether.

As these specific compounds, compounds described in paragraphs 0095 to 0108 of JP 2009-288705 A can also be suitably used in the present invention.

In the present invention, as the polymerizable compound, a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100°C or higher under normal pressure is also preferable. As an example, it is possible to refer to the compounds described in paragraph No. 0227 of JP 2013-29760 A and paragraph Nos. 0254 to 0257 of JP 2008-292970 A, the contents of which are incorporated herein by reference. .

Polymerizable compounds include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) Manufacturing), dipentaerythritol penta (meth)acrylate (KAYARAD D-310 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth)acrylate (KAYARAD DPHA as a commercial product; Nippon Kayaku ( Co., Ltd., A-DPH-12E; Shin-Nakamura Chemical Co., Ltd. product), and compounds in which these (meth)acryloyl groups are bonded through ethylene glycol and propylene glycol residues (for example, SR454, SR499, which are commercially available from Satomer, are preferred. These oligomer types can also be used. In addition, KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.), A-TMMT (pentaerythritol tetraacrylate, Shin-Nakamura Chemical Co., Ltd. product), Aronix M-315, M-313 (Toa Kosei Co., Ltd. product) can also be used. The mode of a preferable polymeric compound is shown below.

The polymerizable compound may have an acid group such as a carboxy group, a sulfonic acid group, and a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a polymerizable compound obtained by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxy group of the aliphatic polyhydroxy compound to give an acid group More preferably, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. As a commercial item, M-305, M-510, M-520, etc. are mentioned as a polybasic acid-modified acrylic oligomer manufactured by Toa Kosei Co., Ltd., for example.

The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, and particularly preferably 5 to 30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the developing dissolution property is good, and when it is 40 mgKOH/g or less, it is advantageous in terms of production and handling. Furthermore, photopolymerization performance is good and curability is excellent.

The polymerizable compound is also a preferred embodiment of a compound having a caprolactone structure.

The compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples include trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, penta Ε-caprolactone-modified polyfunctional obtained by esterifying polyhydric alcohols such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, and trimethylolmelamine, and (meth)acrylic acid and ε-caprolactone (Meth)acrylate is mentioned. Among them, a compound represented by the following formula (Z-1) is preferable.

[Formula 53]

In formula (Z-1), all six Rs are groups represented by the following formula (Z-2), or 1 to 5 of six Rs are groups represented by the following formula (Z-2), and the remainder is It is a group represented by formula (Z-3).

[Chemical Formula 54]

In formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bond.

[Chemical Formula 55]

In formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond.

The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (in the above formula, m = 1, a group represented by formula (Z-2) A compound in which the number of = 2 and R ¹ are all hydrogen atoms), DPCA-30 (in the above formula, m = 1, the number of groups represented by formula (Z-2) = 3, R ¹ are all hydrogen atoms) ), DPCA-60 (in the above formula, m = 1, the number of groups represented by formula (Z-2) = 6, a compound in which R ¹ is all hydrogen atoms), DPCA-120 (in the formula, m = 2, the number of groups represented by the formula (Z-2) = 6, and a compound in which all of R ¹ are hydrogen atoms), and the like.

As the polymerizable compound, a compound represented by the following formula (Z-4) or formula (Z-5) can also be used.

[Formula 56]

In formulas (Z-4) and (Z-5), E is each independently -((CH ₂ ) _y CH ₂ O)-, or -((CH ₂ ) _y CH(CH ₃ )O)- And y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group.

In formula (Z-4), the total number of (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0-10, and the total of each m is an integer of 0-40.

In Formula (Z-5), the total number of (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0-10, and the sum of each n is an integer of 0-60.

In formula (Z-4), the integer of 0-6 is preferable and, as for m, the integer of 0-4 is more preferable.

Moreover, as for the sum of each m, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and the integer of 4-8 is especially preferable.

In formula (Z-5), the integer of 0-6 is preferable and, as for n, the integer of 0-4 is more preferable.

In addition, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.

In addition, -((CH ₂ ) _y CH ₂ O)- or -((CH ₂ ) _y CH(CH ₃ ) O)- in Formula (Z-4) or Formula (Z-5) is the terminal on the oxygen atom side The form bonded to this X is preferable.

The compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more. In particular, in the formula (Z-5), the form in which all six Xs are acryloyl groups is preferable.

Moreover, as the total content in the polymerizable compound of the compound represented by formula (Z-4) or formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

The compound represented by formula (Z-4) or formula (Z-5) is a process of bonding a ring-opening skeleton to pentaerythritol or dipentaerythritol by ring-opening addition reaction, which is a conventionally known process. And, it can be synthesized by a step of introducing a (meth)acryloyl group by reacting, for example, (meth)acryloyl chloride to the terminal hydroxy group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize the compound represented by the formula (Z-4) and (Z-5).

Among the compounds represented by formula (Z-4) or formula (Z-5), pentaerythritol derivatives and/or dipentaerythritol derivatives are more preferred.

Specifically, compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as "exemplary compounds (a) to (f)") are mentioned, and among them, exemplary compounds (a) and (b) , (e), (f) are preferred.

[Chemical Formula 57]

[Chemical Formula 58]

Commercially available products of the polymerizable compounds represented by formulas (Z-4) and (Z-5) include, for example, SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, and Nippon Kayaku Co., Ltd. ) Agent DPCA-60 which is a 6-functional acrylate having 6 pentyleneoxy chains, and TPA-330 which is a trifunctional acrylate having 3 isobutyleneoxy chains.

The polymerizable compound is also preferably an ethylene oxide-modified (meth)acrylate isocyanate. As a commercial item, Aronix M-315, M-313 (manufactured by Toa Kosei Co., Ltd.), NK ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), SR368 (manufactured by Satomer), and the like are mentioned. Further, as the polymerizable compound used in combination with a titanylphthalocyanine pigment, it is preferable that the SP value (Solubility Parameter) is high from the viewpoint of heat resistance. As a polymerizable compound having a high SP value, Aaronix M-315 and M-313 (manufactured by Toa Kosei Co., Ltd.) can be mentioned.

As a polymerizable compound, as described in Japanese Laid-Open Patent Publication No. 48-41708, Japanese Laid-Open Patent Publication No. 51-37193, Japanese Laid-Open Patent Publication No. Hei 2-32293, and Japanese Laid-Open Patent Publication No. Hei 2-16765. , Urethane acrylates, ethylene described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Publication No. 62-39417, and Japanese Publication No. 62-39418 Urethane compounds having an oxide skeleton are also suitable. In addition, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-63-260909, and JP 1-105238 are used. By doing so, it is possible to obtain a colored composition having very excellent photosensitive speed.

As commercially available products, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Corporation), UA-7200 (manufactured by Shin-Nakamura Chemical Industries, Ltd.), DPHA-40H (manufactured by Nippon Kayaku Corporation), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (Kyoeisha Chemical Co., Ltd. product), etc. are mentioned.

<<<polyfunctional thiol compound>>>

The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of accelerating the reaction of the polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanesiols, and particularly preferably a compound having a structure represented by the following formula (T1).

Equation (T1)

[Chemical Formula 59]

(In formula (T1), n represents the integer of 2-4, and L represents a bivalent connecting group.)

In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2, and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and compounds represented by formula (T2) are particularly preferred. The polyfunctional thiol compound can be used singly or in combination.

[Chemical Formula 60]

The content of the polyfunctional thiol compound is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass with respect to the total solid content of the colored composition. Further, the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like.

<<<Compound having an epoxy group>>>

In the present invention, a compound having an epoxy group can also be used as the curable compound.

In the present invention, as the compound having an epoxy group, it is preferable to have two or more epoxy groups in one molecule. By using a compound having two or more epoxy groups in one molecule, it is easy to obtain a cured film excellent in heat resistance. The number of epoxy groups is preferably 2 to 100 per molecule. The upper limit may be set to 10 or less, for example, and may be set to 5 or less.

In the present invention, the compound having an epoxy group is preferably a structure having an aromatic ring and/or an aliphatic ring, and more preferably a structure having an aliphatic ring. It is preferable that the epoxy group is bonded to an aromatic ring and/or an aliphatic ring via a single bond or a linking group. As a linking group, a structure represented by an alkylene group, an arylene group, -O-, -NR'- (R' represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and a hydrogen atom is preferable) , -SO ₂ -, -CO-, -O- and a group containing at least one selected from -S-. In the case of a compound having an aliphatic ring, the epoxy group is preferably a compound formed by directly bonding (single bond) to an aliphatic ring. In the case of a compound having an aromatic ring, the epoxy group is preferably a compound formed by bonding to the aromatic ring through a linking group. The linking group is preferably a group consisting of an alkylene group or a combination of an alkylene group and -O-.

As the compound having an epoxy group, a compound having a structure in which two or more aromatic rings are linked with a hydrocarbon group may be used. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected through the linking group.

In the compound having an epoxy group, the epoxy equivalent (= molecular weight of the compound having an epoxy group / number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 to 400 g/eq, and more preferably 100 to 300 g/eq Do.

The compound having an epoxy group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, and furthermore a molecular weight of less than 1000), or a macromolecule (e.g., a molecular weight of 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 or more) Any of them may be used. As for the weight average molecular weight of the compound which has an epoxy group, 200-100000 are preferable, and 500-500,000 are more preferable. The upper limit of the weight average molecular weight is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1500 or less.

The compound having an epoxy group is a compound described in paragraphs 0034 to 0036 of JP 2013-011869 A, paragraphs 0147 to 0156 of JP 2014-043556 A, and paragraphs 0085 to 0092 of JP 2014-089408 A. You can also use These contents shall be used in this specification. As a commercial item, for example, as a bisphenol A type epoxy resin, jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above, manufactured by DIC Corporation), and the bisphenol F type epoxy resins include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, and DIC Co., Ltd.), LCE-21, RE-602S (above, Nippon Kayaku Co., Ltd.), etc., and as phenol novolac type epoxy resins, jER152, jER154, jER157S70, jER157S65 (above, Mitsubishi Chemical ( Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, manufactured by DIC Corporation), etc., and as cresol novolac type epoxy resins, EPICLON N-660, EPICLON N-665, EPICLON N -670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Corporation), etc., and aliphatic epoxy resins Examples include ADEKA RESIN EP-4080S, copper EP-4085S, copper EP-4088S (above, manufactured by ADEKA Co., Ltd.), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, Copper PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase Chemtex Corporation), etc. In addition, ADEKA RESIN EP-4000S, copper EP-4003S, copper EP-4010S, copper EP-4011S (above, manufactured by ADEKA Co., Ltd.), NC-2000, NC-3000, NC-7300, XD-1000, EPPN -501, EPPN-502 (above, made by ADEKA Co., Ltd.), jER1031S (made by Mitsubishi Chemical Co., Ltd.), etc. are mentioned.

When using a compound having an epoxy group, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass with respect to the total solid content of the colored composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less. The compound having an epoxy group may be used alone or in combination of two or more. When two or more types are used together, it is preferable that the total amount falls within the above range.

Moreover, when a polymerizable compound and a compound having an epoxy group are used in combination, the mass ratio of the polymerizable compound and the compound having an epoxy group is preferably a polymerizable compound: a compound having an epoxy group = 100:1 to 100:400, and 100: 1-100:100 is more preferable.

<<<Photopolymerization initiator>>>

It is preferable that the coloring composition of this invention contains a photoinitiator.

The photoinitiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photoinitiators. For example, it is preferable to have photosensitivity to visible light from the ultraviolet region. Further, an activator that generates an active radical by generating an action with a photo-excited sensitizer may be used, or an initiator that initiates cationic polymerization depending on the type of monomer.

Further, it is preferable that the photopolymerization initiator contains at least one compound having a molar extinction coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).

As a photoinitiator, for example, halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole And oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones. As a halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. The compound described in Japan, 42, 2924 (1969), the compound described in British Patent Publication No. 1388492, the compound described in Japanese Laid-Open Patent Publication No. 53-133428, the compound described in German Patent Publication No. 3337024, J by FC Schaefer et al. Org. Chem.; 29, 1527 (1964), the compound described in Japanese Laid-Open Patent Publication No. 62-58241, the compound described in Japanese Laid-Open Patent Publication No. Hei 5-281728, the compound described in Japanese Laid-Open Patent Publication No. Hei 5-34920, the United States The compound etc. of patent publication 4212976 are mentioned.

In addition, from the viewpoint of exposure sensitivity, trihalomethyltriazine compound, benzyldimethylketal compound, α-hydroxyketone compound, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime Compound, triallylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound and its derivatives, cyclopentadiene-benzene-iron complex and its salt, halomethyloxadiazole compound, 3- A compound selected from the group consisting of aryl substituted coumarin compounds is preferred.

More preferably, a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, an oxime compound, a triallylimidazole dimer, an onium compound, a benzophenone compound, an acetophenone compound, and , At least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds is particularly preferred.

Particularly, when the film of the present invention is used in a solid-state imaging device, it is necessary to form a fine pattern in a sharp shape, so it is important that the film of the present invention is developed without residue in the unexposed portion with curability. From such a viewpoint, it is particularly preferable to use an oxime compound as the photoinitiator. In particular, in the case of forming a fine pattern in a solid-state imaging device, stepper exposure is used for exposure for curing, but this exposure machine is sometimes damaged by halogen, and it is necessary to suppress the addition amount of the photopolymerization initiator to a low level. In view of these points, in order to form a fine pattern like a solid-state imaging device, it is particularly preferable to use an oxime compound as a photoinitiator. Moreover, by using an oxime compound, the discoloration property can be made more favorable.

As a specific example of the photoinitiator, description of paragraphs 0265 to 0268 of JP 2013-29760A can be referred to, for example, and this content is assumed to be incorporated herein.

As a photoinitiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can also be used suitably. More specifically, for example, the aminoacetophenone initiator described in JP-A-10-291969 A and the acylphosphine initiator described in JP-A-4225898 can be used.

As the hydroxyacetophenone initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.

As the aminoacetophenone initiator, commercially available products IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used. As the aminoacetophenone initiator, a compound described in Japanese Patent Application Laid-Open No. 2009-191179 in which an absorption wavelength is matched to a light source such as 365 nm or 405 nm can also be used.

As the acylphosphine initiator, commercially available IRGACURE-819 or DAROCUR-TPO (trade names: all manufactured by BASF) can be used.

As a photoinitiator, more preferably, an oxime compound is mentioned.

As a specific example of the oxime compound, a compound described in JP 2001-233842 A, a compound described in JP 2000-80068 A, and a compound described in JP 2006-342166 A can be used.

As an oxime compound that can be used suitably in the present invention, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one , 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluene Sulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

Also, J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, the compounds described in each publication, etc. are also mentioned.

In commercial products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (above, manufactured by BASF) are also suitably used. In addition, TR-PBG-304 (Changzhou Tronly New Electronic Materials Co., Ltd.), Adeka Arcles NCI-831 (ADEKA), Adeka Arcles NCI -930 (manufactured by ADEKA Co., Ltd.), Adeka optomer N-1919 (manufactured by ADEKA Co., Ltd., photopolymerization initiator 2 described in Japanese Patent Application Laid-Open No. 2012-14052) can also be used.

In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is connected to the N-position of the carbazole ring, compounds described in US Patent Publication No. 7626957 in which a hetero substituent is introduced into a benzophenone moiety, a dye moiety A compound described in Japanese Patent Laid-Open Publication No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced, a ketoxime compound described in WO2009/131189, a triazine skeleton and an oxime skeleton are contained in the same molecule The compound described in US Patent Publication No. 7556910, which has an absorption maximum at 405 nm and has good sensitivity to a g-ray light source, may be used.

Preferably, it is possible to refer to, for example, the description of paragraphs 0274 to 0275 of Japanese Unexamined Patent Application Publication No. 2013-29760, the contents of which are incorporated herein by reference.

Specifically, as an oxime compound, a compound represented by the following formula (OX-1) is preferable. Further, the N-O bond of the oxime may be an oxime compound of the (E) body, an oxime compound of the (Z) body, or a mixture of the (E) body and (Z) body.

[Chemical Formula 61]

In formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

In formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetallic group.

Examples of the monovalent nonmetallic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be substituted with another substituent.

Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group, and the like.

In formula (OX-1), as the monovalent substituent represented by B, an aryl group, heterocyclic group, arylcarbonyl group, or heterocyclic carbonyl group is preferable. These groups may have 1 or more substituents. As a substituent, the substituent mentioned above can be illustrated.

In formula (OX-1), as the divalent organic group represented by A, an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, and an alkynylene group are preferable. These groups may have 1 or more substituents. As a substituent, the substituent mentioned above can be illustrated.

In the present invention, as the photopolymerization initiator, an oxime compound having a fluorine atom (fluorine-containing oxime ester photopolymerization initiator) can also be used. As specific examples of the oxime compound having a fluorine atom, the compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in JP 2014-500852 A, and the compounds described in JP 2013-164471 A. (C-3), etc. are mentioned. This content is assumed to be incorporated in the present specification.

In the present invention, the fluorinated oxime ester photoinitiator is preferably a compound represented by the following formula (OX-100).

[Formula 62]

In the formula (OX-100), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent, R ¹ represents an aryl group having a group containing a fluorine atom, and R ² and R ³ represents an alkyl group or an aryl group each independently.

Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent.

The aromatic hydrocarbon ring may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the ring of the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10. As for the aromatic hydrocarbon ring, a benzene ring and a naphthalene ring are preferable. Especially, it is preferable that at least one of Ar ¹ and Ar ² is a benzene ring, and it is more preferable that Ar ¹ is a benzene ring. Ar ² is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.

As a substituent which Ar ¹ and Ar ² may have, an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 , -NHSO ₂ R ^X1, etc. . R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.

The alkyl group as a substituent and the number of carbon atoms of the alkyl group represented by R ^X1 and R ^X2 are preferably 1 to 20. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable. In the alkyl group, some or all of the hydrogen atoms may be substituted with halogen atoms (preferably, fluorine atoms). Further, in the alkyl group, some or all of the hydrogen atoms may be substituted with the above substituents.

The number of carbon atoms of the aryl group as a substituent and the aryl group represented by R ^X1 and R ^X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring. Further, in the aryl group, some or all of the hydrogen atoms may be substituted with the above substituents.

The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring may be sufficient as it. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. Moreover, in the heterocyclic group, some or all of the hydrogen atoms may be substituted with the said substituent.

Ar ¹ is preferably an unsubstituted aromatic hydrocarbon ring. Ar ² may be an unsubstituted aromatic hydrocarbon ring or an aromatic hydrocarbon ring having a substituent. As a substituent, -COR ^X1 is preferable. R ^X1 is preferably an alkyl group, an aryl group, or a heterocyclic group, and more preferably an aryl group. The aryl group may have a substituent or may be unsubstituted. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

R ¹ represents an aryl group having a group containing a fluorine atom.

The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (a fluorine-containing alkyl group) and/or a group containing an alkyl group having a fluorine atom (a fluorine-containing group).

The fluorinated group is -OR ^X11 , -SR ^X11 , -COR ^X11 , -COOR ^X11 , -OCOR ^X11 , -NR ^X11 R ^X12 , -NHCOR ^X11 , -CONR ^X11 R ^X12 , -NHCONR ^X11 R ^X12 , -NHCOOR ^X11 , At least one group selected from -SO ₂ R ^X11 , -SO ₂ OR ^X11 and -NHSO ₂ R ^X11 is preferable, and -OR ^X11 is more preferable. R ^X11 represents a fluorinated alkyl group, and R ^X12 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, an aryl group or a heterocyclic group.

The group containing a fluorine atom is preferably a fluorinated alkyl group and/or -OR ^X11 .

As for the carbon number of a fluorinated alkyl group, 1-20 are preferable, 1-15 are more preferable, 1-10 are more preferable, and 1-4 are especially preferable. The fluorinated alkyl group may be linear, branched or cyclic, but linear or branched is preferable.

As for the fluorinated alkyl group, the substitution ratio of the fluorine atom is preferably 40 to 100%, more preferably 50 to 100%, and still more preferably 60 to 100%.

The alkyl group, aryl group and heterocyclic group represented by R ^X12 are the same as those described for the alkyl group, aryl group and heterocyclic group represented by R ^X1 and R ^X2 .

R ² represents an alkyl group or an aryl group, and an alkyl group is preferable. The alkyl group and the aryl group may be unsubstituted or may have a substituent. As a substituent, the above-mentioned substituent is mentioned.

The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable.

The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

R ³ represents an alkyl group or an aryl group, and an alkyl group is preferable. The alkyl group and the aryl group may be unsubstituted or may have a substituent. As a substituent, the above-mentioned substituent is mentioned.

The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable.

The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

As a specific example of the compound represented by formula (OX-100), the following compound is mentioned, for example.

[Chemical Formula 63]

In the present invention, as the photoinitiator, an oxime initiator having a nitro group can be used. As an oxime initiator having a nitro group, a compound represented by the following formula (OX-200) can be mentioned.

Formula (OX-200)

[Formula 64]

In the formula, X ¹ , X ³ and X ⁶ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and X ² is an alkyl group, an aryl group, an aralkyl group or a heterocyclic group Represents, X ⁴ and X ⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , COSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom or a hydroxyl group is represented. R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group. a and b are each independently 0-3.

The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, more preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but linear or branched is preferable.

The number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

7-30 are preferable and, as for the carbon number of an aralkyl group, 7-20 are more preferable. The aryl group may be a monocyclic ring or a condensed ring.

The heterocyclic group may be a monocyclic ring or a condensed ring may be sufficient as it. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and more preferably 3 to 12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom.

The alkyl group, aryl group, aralkyl group, and heterocyclic group may have a substituent or may be unsubstituted. Examples of the substituent include the substituents described for the substituents that Ar ¹ and Ar ² in the above formula (1) may have.

Specific examples of the oxime initiator having a nitro group include compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, 0070 to 0079 of JP 2014-137466 A, or adeca Ackles NCI-831 (made by ADEKA Co., Ltd.) is mentioned.

In the present invention, as a photopolymerization initiator, a compound represented by the following formula (OX-300) or (OX-400) can also be used.

[Formula 65]

In formula (OX-300), R ¹ and R ² are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 to 30 carbon atoms. Represents an arylalkyl group of and R ¹ and R ² are phenyl groups, phenyl groups may be bonded to each other to form a fluorene group, and R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 6 carbon atoms A to 30 aryl group, a C 7 to C 30 arylalkyl group or a C 4 to C 20 heterocyclic group is represented, and X represents a direct bond or a carbonyl group.

In the formula (OX-400), R ^1, R ^2, R ³ and R ^4, and R ^1, R ^2, R ³ and R ⁴ with the consent of the formula (OX-300), R ⁵ is -R ⁶ , -OR ⁶ , -SR ⁶ , -COR ⁶ , -CONR ⁶ R ⁶ , -NR ⁶ COR ⁶ , -OCOR ⁶ , -COOR ⁶ , -SCOR ⁶ , -OCSR ⁶ , -COSR ⁶ , -CSOR ⁶ , -CN, a halogen atom or a hydroxyl group is represented, and R ⁶ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0-4.

In the above formulas (OX-300) and (OX-400), R ¹ and R ² are each independently preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group or a phenyl group. R ³ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group. R ⁴ is preferably an alkyl group or a phenyl group having 1 to 6 carbon atoms. R ⁵ is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group. X is preferably a direct bond.

Specific examples of the compound represented by the formula (OX-300) and the formula (OX-400) include, for example, the compounds described in paragraphs 0076 to 0079 of JP 2014-137466A. This content is assumed to be incorporated in the present specification.

In the present invention, as a photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. As a specific example, OE-01 to OE-75 described in International Publication WO2015/036910 are mentioned.

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited thereto.

[Formula 66]

The oxime compound is preferably a compound having an absorption maximum in a wavelength region of 350 nm to 500 nm, and a compound having an absorption maximum in a wavelength region of 360 nm to 480 nm is more preferable. Further, the oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g/L using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent.

The photoinitiators used in the present invention may be used singly or in combination of two or more.

In the present invention, it is also preferable that the photopolymerization initiator uses an aminoacetophenone compound and an oxime compound in combination. According to this aspect, the residue after pattern formation can be made favorable.

The content of the photoinitiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1 to 20% by mass with respect to the total solid content of the colored composition. In this range, better sensitivity and pattern formation are obtained. The coloring composition of this invention may contain only one type and may contain two or more types of photoinitiators. When it contains two or more types, it is preferable that the total amount becomes the said range.

<<<Organic solvent>>>

The coloring composition of this invention can contain an organic solvent. The organic solvent is basically not particularly limited as long as it satisfies the solubility of each component and the applicability of the colored composition, but is preferably selected in consideration of the applicability and safety of the colored composition.

As an example of an organic solvent, the following are mentioned, for example.

As esters, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate , Methyl lactate, ethyl lactate, alkyl oxyacetate (e.g. methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, Ethyl oxyacetate)), 3-oxypropionate alkyl esters (eg, 3-oxypropionate methyl, 3-oxypropionate ethyl, etc. (eg 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3- Methyl ethoxypropionate, ethyl 3-ethoxypropionate, etc.), 2-oxypropionic acid alkyl esters (e.g., 2-oxypropionate methyl, 2-oxypropionate ethyl, 2-oxypropionate propyl, etc.) Methyl oxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-oxy-2-methyl methylpropionate and 2-oxy-2- Ethyl methylpropionate (e.g., 2-methoxy-2-methylpropionate methyl, 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2- Methyl oxobutanoate, ethyl 2-oxobutanoate, etc. As ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ter, Methyl Cellosolve Acetate, Ethyl Cellosolve Acetate, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl Ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., as ketones, such as methyl ethyl ketone, cyclohexanone, cyclopentanone , 2-heptanone, 3-heptanone, etc., as aromatic hydrocarbons, For example, toluene, xylene, etc. are mentioned suitably.

Organic solvents may be used alone or in combination of two or more.

When two or more organic solvents are used in combination, particularly preferably, the above methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycoldimethyl ether , Butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate It is a mixed solution composed of two or more kinds.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol/L or less, and more preferably does not substantially contain a peroxide.

In the present invention, it is preferable to use an organic solvent having a small metal content, and the metal content of the organic solvent is preferably 10 ppb or less, for example. If necessary, a ppt-level organic solvent may be used, and such a high-purity solvent is provided by Toyo Kosei, for example (Kagaku Kogyo Nippo, November 13, 2015).

As a method of removing impurities such as metals from the organic solvent, for example, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter may be mentioned. As a filter pore diameter in filtration using a filter, a pore size of 10 nm or less is preferable, 5 nm or less is more preferable, and 3 nm or less is still more preferable. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable.

The organic solvent may contain isomers (compounds of different structures with the same number of atoms). Moreover, only 1 type may be contained and multiple types may be contained as an isomer.

As the amount of the organic solvent contained in the coloring composition, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and more preferably 25 to 75% by mass with respect to the total amount of the coloring composition. .

<<<polymerization inhibitor>>>

The colored composition of the present invention may contain a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the colored composition.

As a polymerization inhibitor, hydroquinone, paramethoxyphenol, di-tert-butyl-paracresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert) -Butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt, etc. are mentioned. Among them, paramethoxyphenol is preferred.

The addition amount of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the mass of the colored composition.

<<<Substrate adhesive>>>

The colored composition of the present invention can contain a substrate adhesive.

It is preferable to use a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent as the substrate adhesion agent.

Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, and γ-acryloxypropyltri Ethoxysilane, γ-mercaptopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, phenyl trimethoxysilane, and the like. Among them, γ-methacryloxypropyltrimethoxysilane is preferable as the substrate adhesive.

In addition, the silane coupling agent is methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and n-propyltrimethoxysilane. Silane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis (trimethoxy Silyl) hexane, trifluoropropyltrimethoxysilane, hexamethyldisilazein, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxy Silane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane , 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amino Ethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl- Hydrochloride salt of butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, tris-(trime) Toxisilylpropyl) isocyanurate, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl) ) Tetrasulfide, 3-isocyanate propyl triethoxysilane, etc. are mentioned. Further, in addition to the above, alkoxy oligomers can be used. Moreover, the following compounds can also be used.

[Chemical Formula 67]

As a commercial item, Shin-Etsu Silicone Co., Ltd. product KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066 , KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, KBM-7103, SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM -403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903 , KBE-9103, KBM-573, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-40-1053, X-41-1059A, X -41-1056, X-41-1805, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40 -9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X -40-9238, etc. are mentioned.

Further, as the silane coupling agent, a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in a molecule and a hydrolyzable group bonded to a silicon atom may be used.

The hydrolyzable group refers to a substituent that is directly connected to a silicon atom and capable of generating a siloxane bond by a hydrolysis reaction and/or a condensation reaction. As a hydrolyzable group, a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group are mentioned, for example. When the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less. In particular, an alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is preferable.

The silane coupling agent Y may have at least one silicon atom in its molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different. Atoms and substituents that can be bonded include a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an amino group substituted with an alkyl group and/or an aryl group, a silyl group, a carbon number of 1 In the above, 20 alkoxy groups and aryloxy groups may be mentioned. These substituents are also silyl group, alkenyl group, alkynyl group, aryl group, alkoxy group, aryloxy group, thioalkoxy group, an amino group substitutable with an alkyl group and/or aryl group, a halogen atom, a sulfonamide group, an alkoxycarbonyl group , An amide group, a urea group, an ammonium group, an alkyl ammonium group, a carboxy group, or a salt thereof, a sulfo group, or a salt thereof.

In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.

The silane coupling agent Y may contain a group represented by formula (Z).

Formula (Z) *-Si(R ^z1 ) _3-m (R ^z2 ) _m

R ^z1 represents an alkyl group, R ^z2 represents a hydrolyzable group, and m represents an integer of 1 to 3. The number of carbon atoms in the alkyl group represented by R ^z1 is preferably 1 to 5, and more preferably 1 to 3. The definition of the hydrolyzable group represented by R ^z2 is as described above.

The silane coupling agent Y has at least one nitrogen atom in its molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom has at least one organic group as a substituent. desirable. In addition, as the structure of the amino group, it may be present in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may be present as a substituted amino group such as aniline. Here, examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof. These may further have a substituent, and examples of the substituent that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, a sulfonamide group, an alkoxycarbo And a nil group, a carbonyloxy group, an amide group, a urea group, an alkyleneoxy group, an ammonium group, an alkyl ammonium group, a carboxy group, or a salt thereof, a sulfo group.

Moreover, it is preferable that a nitrogen atom is bonded with a curable functional group through an arbitrary organic linking group. As a preferable organic linking group, the nitrogen atom mentioned above and the substituent which can be introduced into the organic group bonded to it are mentioned.

The curable functional groups contained in the silane coupling agent Y are (meth)acryloyloxy group, epoxy group, oxetanyl group, isocyanate group, hydroxy group, amino group, carboxy group, thiol group, alkoxysilyl group, methylol group , Vinyl group, (meth)acrylamide group, styryl group, and preferably at least one selected from the group consisting of maleimide groups, and selected from the group consisting of (meth)acryloyloxy group, epoxy group, and oxetanyl group It is more preferable that it is at least 1 type, and at least 1 type selected from the group consisting of a (meth)acryloyloxy group, an epoxy group, and an oxetanyl group is more preferable.

In the silane coupling agent Y, it is sufficient to have at least one curable functional group in one molecule, but it is also possible to take an aspect having two or more curable functional groups, and it is preferable to have 2 to 20 curable functional groups from the viewpoint of sensitivity and stability, It is more preferable to have 4 to 15, and most preferably, it is an aspect having 6 to 10 curable functional groups in the molecule.

As the silane coupling agent Y, the compound represented by the following formula (Y) is mentioned, for example.

Formula (Y) (R ^y3 ) _n -LN-Si(R ^y1 ) _3-m (R ^y2 ) _m

R ^y1 represents an alkyl group, R ^y2 represents a hydrolyzable group, R ^y3 represents a curable functional group,

LN represents a (n+1) valent linking group having a nitrogen atom,

m represents the integer of 1-3, and n represents the integer of 1 or more.

R ^y1 , R ^y2 and m in the formula (Y) have the same ^definitions as R ^z1 , R ^z2 and m in the formula (Z), and the preferred ranges are also the same.

R ^y3 in formula (Y) represents a curable functional group. Examples of the curable functional group include the groups described for the curable functional group contained in the silane coupling agent Y.

N in Formula (Y) represents an integer of 1 or more. As for the upper limit, 20 or less are preferable, for example, 15 or less are more preferable, and 10 or less are still more preferable. The lower limit is, for example, preferably 2 or more, more preferably 4 or more, and still more preferably 6 or more. Moreover, n can also be set to 1.

LN in formula (Y) represents a group having a nitrogen atom.

As a group having a nitrogen atom, at least one selected from the following formulas (LN-1) to (LN-4), or the following formulas (LN-1) to (LN-4), -CO-, -CO ₂ Groups consisting of at least one combination selected from -, -O-, -S- and -SO ₂ -are mentioned. The alkylene group may be either linear or branched. The alkylene group and the arylene group may be unsubstituted or have a substituent. Examples of the substituent include a halogen atom and a hydroxy group.

[Chemical Formula 68]

In the formula, * represents a connecting hand.

As a specific example of a silane coupling agent Y, the following compounds are mentioned, for example. In the formula, Et represents an ethyl group. In addition, the compounds described in paragraphs 0018 to 0036 of JP 2009-288703 A can be mentioned, and the contents are intended to be incorporated in the present specification.

[Formula 69]

The content of the substrate adhesive is preferably 0.1 to 30% by mass, more preferably 0.5 to 20% by mass, and particularly preferably 1 to 10% by mass with respect to the total solid content of the colored composition.

<<<surfactant>>>

The colored composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.

By containing a fluorine-based surfactant in the coloring composition of the present invention, the liquid properties (especially, fluidity) when prepared as a coating liquid are improved, and the uniformity of the coating thickness and liquid-forming properties can be further improved. have.

That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is lowered, thereby improving the wettability of the surface to be coated, and the application to the surface to be coated. The performance is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with a small thickness variation.

The fluorine content rate in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of the thickness of the coating film and liquid-forming properties, and has good solubility in the composition.

As a fluorine-based surfactant, for example, Megapak F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above, DIC Co., Ltd.), Fluorad FC430, FC431, FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC -381, SC-383, S393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like. As the fluorine-based surfactant, a compound described in paragraphs 0117 to 0132 of JP2011-132503A, and a compound described in paragraphs 0015 to 0158 of JP 2015-117327 can also be used. A block polymer can also be used as a fluorine-based surfactant, and as a specific example, the compound of Unexamined-Japanese-Patent No. 2011-89090 is mentioned, for example.

The fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably ethyleneoxy group, propyleneoxy group) of 2 or more (preferably 5 or more). ) A fluorinated polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.

[Chemical Formula 70]

The weight average molecular weight of the said compound is 14,000, for example.

Further, a fluorinated polymer having an ethylenic unsaturated group in the side chain can also be used as a fluorine-based surfactant. As specific examples, the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP 2010-164965 A, for example, Megapak RS-101, RS-102, RS-718K, etc. manufactured by DIC can be mentioned.

Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene. Lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol die Stearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Solspurs 20000 (Nihon Lubri Sol Co., Ltd. product) etc. are mentioned. Moreover, NCW-101, NCW-1001, NCW-1002 manufactured by Wako Junyaku High School can also be used.

Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), ( Meth)acrylic acid (co)polymer polyflo No. 75, No. 90, No. 95 (made by Kyoeisha Chemical Co., Ltd.), W001 (made by Yusho Co., Ltd.), etc. are mentioned.

Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.).

Examples of silicone surfactants include Toray Silicon DC3PA, Toray Silicon SH7PA, Toray Silicon DC11PA, Toray Silicon SH21PA, Toray Silicon SH28PA, Toray Silicon SH29PA, Toray Silicon SH30PA, Toray Silicon SH8400 (above, Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) Article), BYK307, BYK323, BYK330 (above, made by Big Chemie), and the like.

Only 1 type may be used for surfactant, and 2 or more types may be combined.

The addition amount of the surfactant is preferably 0.001 to 2.0% by mass and more preferably 0.005 to 1.0% by mass with respect to the total mass of the coloring composition.

<<<other ingredients>>>

The coloring composition of the present invention is a thermal polymerization initiator such as an azo compound or a peroxide compound, a thermal polymerization component, an ultraviolet absorber such as alkoxybenzophenone, a plasticizer such as dioctylphthalate, a developability improving agent such as a low molecular weight organic carboxylic acid, and the like, It may contain various additives such as external fillers, antioxidants, and anti-aggregation agents.

In addition, after development, a thermosetting agent may be added to increase the degree of curing of the film by post heating. Examples of the thermosetting agent include thermal polymerization initiators such as azo compounds and peroxides, novolac resins, resol resins, epoxy compounds, and styrene compounds.

Depending on the raw material used, the composition may contain a metal element, but from the viewpoint of suppressing the occurrence of defects, the content of the group 2 element (calcium, magnesium, etc.) in the coloring composition is preferably 50 ppm or less, and is controlled to 0.01 to 10 ppm. It is desirable to do. Moreover, it is preferable that the total amount of inorganic metal salts in a coloring composition is 100 ppm or less, and it is more preferable to control to 0.5-50 ppm.

(Method of preparing a colored composition)

The colored composition of the present invention can be prepared by mixing the above-described components.

When preparing the coloring composition, each component may be blended together, or may be blended sequentially after dissolving and dispersing each component in a solvent. In addition, the order of addition or working conditions at the time of compounding are not particularly limited. For example, all components may be simultaneously dissolved and dispersed in a solvent to prepare a composition.If necessary, each component is appropriately used as two or more solutions and dispersions, and these are mixed at the time of use (at the time of application) to form a composition. You may prepare.

In addition, when a pigment is used as a colorant or infrared absorber that blocks light in the visible region, the pigment is dispersed with other components such as a resin, an organic solvent, and a pigment derivative, if necessary, to prepare a pigment dispersion, and the obtained pigment It is preferable to prepare the dispersion by mixing it with other components of the coloring composition.

The pigment dispersion liquid may be prepared by separately dispersing a colorant for blocking light in the visible region and an infrared absorber, respectively, or may be prepared by dispersing (co-dispersing) a colorant for blocking light in the visible region and an infrared absorber at the same time. In particular, when using a pyrrolopyrrole compound (preferably a pyrrolopyrrole compound represented by formula (1)) as an infrared absorber, it is preferable to co-disperse with a chromatic colorant. According to this aspect, the dispersion stability of the pyrrolopyrrole compound can be improved.

When preparing the colored composition, it is preferable to filter with a filter for the purpose of removing foreign matters or reducing defects. The filter is not particularly limited and can be used as long as it has been conventionally used for filtration applications or the like. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g. nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) ( Filters using materials such as high-density and ultra-high molecular weight polyolefin resins) are mentioned. Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably about 0.01 to 7.0 µm, preferably about 0.01 to 3.0 µm, and more preferably about 0.05 to 0.5 µm. By setting it as this range, it becomes possible to reliably remove fine foreign matter which inhibits preparation of a uniform and smooth composition in a subsequent process. In addition, it is also preferable to use a fibrous filter material, and examples of the filter material include polypropylene fiber, nylon fiber, glass fiber, and the like, specifically SBP type series (SBP008, etc.) manufactured by Rocky Techno, TPR type series ( TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) filter cartridges are available.

When using a filter, other filters may be combined. In that case, filtering by the first filter may be performed only once or may be performed twice or more.

Moreover, you may combine 1st filters of different pore diameters within the above-mentioned range. The pore diameter here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, Nippon Paul Corporation (DFA4201NXEY, etc.), Advantech Toyo Corporation, Nippon Integras Corporation (formerly Nihon Microlis Corporation) or Kitz Micro Filter, etc. You can select from various filters provided.

The second filter may be formed of the same material as the first filter described above.

For example, filtering by the first filter may be performed only with the dispersion, and after mixing other components, the second filtering may be performed.

It is preferable that the coloring composition of this invention satisfies at least 1 or more spectral characteristics among the following (1)-(5).

(1) When a film having a film thickness of 1 μm after drying is formed, the maximum value of the transmittance of light in the thickness direction of the film in the range of 400 to 830 nm is 20% or less, and in the range of 1000 to 1300 nm. The minimum value is more than 70%. 20% or less are more preferable, and, as for the maximum value in the range of a wavelength of 400-830 nm, 10% or less are especially preferable. As for the minimum value in the range of a wavelength of 1000-1300 nm, 70% or more are more preferable, and 80% or more are especially preferable.

(2) When forming a film having a film thickness of 2 μm after drying, the maximum value of the transmittance of light in the thickness direction of the film in the range of 400 to 830 nm is 20% or less, and in the range of 1000 to 1300 nm. The minimum value is more than 70%. 20% or less are more preferable, and, as for the maximum value in the range of a wavelength of 400-830 nm, 10% or less are especially preferable. As for the minimum value in the range of a wavelength of 1000-1300 nm, 70% or more are more preferable, and 80% or more are especially preferable.

(3) When a film having a film thickness of 3 μm after drying is formed, the maximum value of the transmittance of light in the thickness direction of the film in the range of 400 to 830 nm is 20% or less, and in the range of 1000 to 1300 nm. The minimum value is more than 70%. 20% or less are more preferable, and, as for the maximum value in the range of a wavelength of 400-830 nm, 10% or less are especially preferable. As for the minimum value in the range of a wavelength of 1000-1300 nm, 70% or more are more preferable, and 80% or more are especially preferable.

(4) When a film having a film thickness of 5 μm after drying is formed, the maximum value of the transmittance of light in the thickness direction of the film in the range of 400 to 830 nm is 20% or less, and in the range of 1000 to 1300 nm. The minimum value is more than 70%. 20% or less are more preferable, and, as for the maximum value in the range of a wavelength of 400-830 nm, 10% or less are especially preferable. As for the minimum value in the range of a wavelength of 1000-1300 nm, 70% or more are more preferable, and 80% or more are especially preferable.

(5) When forming a film with a film thickness of 2.4 μm after drying, the maximum value of the transmittance of light in the thickness direction of the film in the range of 400 to 830 nm is 20% or less, and in the range of 1000 to 1300 nm The minimum value of is 70% or more. 20% or less are more preferable, and, as for the maximum value in the range of a wavelength of 400-830 nm, 10% or less are especially preferable. As for the minimum value in the range of a wavelength of 1000-1300 nm, 70% or more are more preferable, and 80% or more are especially preferable.

Moreover, in at least one of the ranges of the film thickness described above, the minimum value A of the absorbance in the range of 400 to 830 nm of wavelength is preferably 0.1 to 5, and more preferably 0.3 to 3, for example. Moreover, as for the maximum value B of the absorbance in the range of a wavelength of 1000-1300 nm, 0.01-0.5 are preferable, and 0.02-0.3 are more preferable, for example.

<membrane>

Next, the film in the present invention will be described.

The film of the present invention is formed by curing the colored composition of the present invention described above. The membrane of the present invention is preferably used as a color filter. In particular, it can be preferably used as an infrared transmission filter.

It is preferable that the film of the present invention has the following spectral properties (1) and/or (2). According to this aspect, it is possible to make a film capable of transmitting infrared rays (preferably, light having a wavelength of 900 nm or more) in a state where there is little noise derived from visible light.

(1): The maximum value of the transmittance of light in the film thickness direction in the range of 400 to 830 nm is 20% or less, and the minimum value of the transmittance of light in the thickness direction of the film in the range of 1000 to 1300 nm It is preferable that it is 70% or more. The maximum value of the transmittance of light in the thickness direction of the film in the range of a wavelength of 400 to 830 nm is preferably 20% or less, and more preferably 10% or less. The minimum value of the transmittance of light in the thickness direction of the film in the range of a wavelength of 1000 to 1300 nm is preferably 70% or more, and more preferably 80% or more.

(2): The maximum value of the transmittance of light in the thickness direction of the film in the range of 450 to 650 nm is 20% or less, the transmittance of the light of the wavelength 835 nm in the thickness direction of the film is 20% or less, the thickness of the film It is preferable that the minimum value of the transmittance of light in the direction in the range of a wavelength of 1000 to 1300 nm is 70% or more. The maximum value of the transmittance of light in the thickness direction of the film in the wavelength range of 450 to 650 nm is preferably 20% or less, and more preferably 10% or less. It is preferable that it is 50% or less, and, as for the maximum value in the range of wavelength 650-835 nm of light transmittance in the thickness direction of a film, 30% or less is more preferable. The transmittance of light having a wavelength of 835 nm in the thickness direction of the film is preferably 20% or less, and more preferably 10% or less. It is preferable that the minimum value of the transmittance of light in the thickness direction of the film in the range of a wavelength of 1000 to 1300 nm is 70% or more, and more preferably 80% or more.

The spectral characteristic of the film of the present invention is a value obtained by measuring the transmittance in a range of 300 to 1300 nm using an ultraviolet visible near-infrared spectrophotometer (U-4100 manufactured by Hitachi High Technologies).

The film thickness of the film of the present invention is not particularly limited, but is preferably 0.1 to 20 µm, and more preferably 0.5 to 10 µm.

<Pattern formation method, color filter, and manufacturing method of color filter>

Next, the pattern formation method and the color filter in the present invention will be described in detail through the manufacturing method. Further, a method of manufacturing a color filter using the pattern forming method of the present invention will be described.

The pattern formation method of the present invention comprises a step of forming a colored composition layer on a support by using a colored composition, a step of exposing the colored composition layer in a pattern shape, and a step of developing and removing an unexposed portion to form a colored pattern. Include.

Such a pattern formation method is used for manufacturing a color filter. That is, in the present invention, a method for manufacturing a color filter including the pattern forming method of the present invention is also disclosed. Hereinafter, these details will be described.

<<Process of forming a colored composition layer>>

In the step of forming a colored composition layer, a colored composition layer is formed by applying the colored composition of the present invention on a support.

Examples of the support include a substrate made of a material such as silicon, alkali-free glass, soda glass, Pyrex (registered trademark) glass, and quartz glass. On these substrates, a charge-coupled device (CCD), a complementary metal oxide film semiconductor (CMOS), a transparent conductive film, or the like may be formed. In addition, in some cases, a black matrix is formed to isolate each pixel. On the support, if necessary, an undercoat layer may be provided for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.

As a method of applying the colored composition of the present invention onto a support, various coating methods such as slit coating, ink jet method, rotation coating (spin coating), casting coating, roll coating, and screen printing method can be applied.

It is preferable to dry (pre-bak) the colored composition layer applied on the support body.

The prebaking temperature is preferably 150°C or less, more preferably 120°C or less, more preferably 100°C or less, and particularly preferably 90°C or less. The lower limit can be, for example, 50°C or higher. By performing the prebaking at 150°C or less, for example, in the case where the photoelectric conversion film of the image sensor is made of an organic material, these characteristics can be more effectively maintained.

The prebaking time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Heating can be performed by a hot plate or an oven.

The thickness of the colored layer after drying (after prebaking) is preferably 0.55 to 10 μm. The upper limit is, for example, more preferably 7 μm or less, and still more preferably 5 μm or less. The lower limit is, for example, more preferably 0.60 μm or more, more preferably 0.70 μm or more, and particularly preferably 0.80 μm or more.

<<exposure process>>

Next, the colored composition layer is exposed in a pattern shape (exposure process). For example, pattern exposure can be performed by exposing the colored composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, the exposed part can be hardened.

As the radiation (light) that can be used at the time of exposure, ultraviolet rays such as g-rays and i-rays are particularly preferably used (especially preferably i-rays). Irradiation dose (exposure dose) is 30 ~ 1500mJ / cm ² is preferred, and, 50 ~ 1000mJ / cm ² are more preferred, and, 80 ~ 500mJ / cm ² is particularly preferred.

The oxygen concentration at the time of exposure can be appropriately selected, for example, in a low-oxygen atmosphere in which the oxygen concentration is 19% by volume or less (for example, preferably 15% by volume or less, more preferably 5% by volume or less, more preferably It may be exposed in substantially oxygen-free), and under a high oxygen atmosphere with an oxygen concentration of more than 21% by volume (for example, preferably 22% by volume or more, more preferably 30% by volume or more, more preferably 50% by volume) % Or more). Also roughness of exposure energy and can be appropriately ^{set, 1000W / m 2 ~ 100000W /} m 2 ( for example, preferably 5000W / m ^2, and more preferably at 15000W / m ² or more, more preferably 35000W /m ² or more). Oxygen concentration and exposure illuminance may be combined as appropriate, and the conditions, for example, roughness on the oxygen concentration of 10 volume% 10000W / m ^2, an oxygen concentration in the roughness volume of 25% 25000W / m ² and the like.

<<Development process>>

Next, the unexposed portion is developed and removed to form a pattern. The development and removal of the unexposed part can be performed using a developer. Thereby, the colored composition layer of the unexposed part in the exposure step elutes into the developer, and only the photocured part remains.

The developing method may be any of a spray method, a shower method, a spray method, a puddle method, and the like, and a swing method, a spin method, an ultrasonic method, or the like may be combined with these.

Before contacting the developer, the surface to be developed may be wetted with water or the like in advance to prevent uneven development.

As the developer, an organic alkali developer is preferable, which does not cause damage to the underlying solid-state imaging device or circuit.

The temperature of the developer is preferably 20 to 30°C, for example. The developing time is preferably 20 to 180 seconds. Further, in order to improve the residue removal property, the step of shaking off the developer every 60 seconds and further supplying the developer may be repeated several times.

Examples of the alkali agent used in the developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and organic alkaline compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene. An alkaline aqueous solution diluted with pure water so that the concentration of these alkali agents is 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as a developer.

Moreover, you may use an inorganic alkali for a developer. As an inorganic alkali, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, etc. are preferable, for example.

Moreover, you may use a surfactant for a developer. Examples of the surfactant include surfactants described in the above-described coloring composition, and nonionic surfactants are preferred. When the developer contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.01 to 1.0% by mass, based on the total mass of the developer.

In addition, in the case of using a developer comprising such an alkaline aqueous solution, it is generally preferable to wash (rinse) with pure water after development.

In the present invention, after drying after the developing step, a curing step of curing by heat treatment (post bake) or post exposure may be performed.

Post-baking is a heat treatment after development to complete curing. The heating temperature is preferably 100 to 240°C, and more preferably 200 to 240°C, for example. In addition, when an organic electroluminescence (organic EL) element is used as the light emitting light source, or when the photoelectric conversion film of the image sensor is made of an organic material, it is preferably 150°C or less, more preferably 120°C or less, and 100°C or less. Is more preferable, and 90 degreeC or less is especially preferable. The lower limit can be, for example, 50°C or higher.

The post-baking treatment can be performed continuously or in a batch manner using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so that the film after development becomes the above conditions.

In the case of using light, it can be performed by g-ray, h-ray, i-ray, excimer laser such as KrF or ArF, electron beam, X-ray, etc., but it is preferable to perform it at a low temperature of about 20 to 50°C with a conventional high-pressure mercury lamp. , The irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. In the case of combined use of post-exposure and post-heating, it is preferable to perform post-exposure first.

By performing each step described above, a color filter is produced.

In addition, a color filter may be configured only with colored pixels exhibiting specific spectral properties of the present invention, colored pixels exhibiting the above-described spectral properties, and colored pixels such as red, green, blue, magenta, yellow, cyan, black, colorless, etc. You may configure the color filter which has. When configuring a color filter together with pixels of different colors, colored pixels exhibiting specific spectral characteristics of the present invention may be provided first or may be provided later.

In the pattern formation method of the present invention, in order to efficiently clean the clogging of the nozzle of the discharging part of the coating device or the pipe part, and contamination caused by adhesion, sedimentation, and drying of the composition into the applicator, the solvent related to the colored composition of the present invention It is preferable to use it as a cleaning liquid. In addition, Japanese Unexamined Patent Publication No. Hei 7-128867, Japanese Unexamined Patent Publication No. 7-146562, Japanese Unexamined Patent Publication No. 8-278637, Japanese Unexamined Patent Publication No. 2000-273370, Japanese Unexamined Patent Publication No. 2006-85140, Japan The cleaning liquids described in Unexamined Patent Publication No. 2006-291191, Unexamined Japanese Patent No. 2007-2101, Unexamined Japanese Patent 2007-2102, and 2007-281523 can be suitably used.

Among the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.

These solvents may be used alone or in combination of two or more. When mixing two or more types, it is preferable to mix a solvent having a hydroxy group and a solvent not having a hydroxy group. The mass ratio of the solvent having a hydroxy group and the solvent not having a hydroxy group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. As a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), it is particularly preferred that the ratio is 60/40. Further, in order to improve the permeability of the cleaning liquid to contaminants, a surfactant related to the coloring composition of the present invention described above may be added to the cleaning liquid.

<Solid image sensor>

The solid-state imaging device of the present invention has the color filter of the present invention described above. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration having the color filter of the present invention and functions as a solid-state imaging device. For example, the following configurations are mentioned.

On the support, a plurality of photodiodes constituting the light-receiving area of a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon, etc. are provided, and only the light receiving portion of the photodiode is provided on the photodiode and the transfer electrode. It has a light-shielding film made of tungsten or the like opened, and has a device protective film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and a photodiode light-receiving portion on the light-shielding film, and a color filter for a solid-state image pickup device of the present invention on the device protective film Configuration.

Further, a configuration including a condensing means (for example, a microlens or the like, hereinafter the same) under the color filter (the side closer to the support) as the device protective film, or a configuration including a condensing means on the color filter may be used.

<Infrared ray sensor>

The infrared sensor of the present invention has the color filter of the present invention. The configuration of the infrared sensor of the present invention is a configuration having the color filter of the present invention, and there is no particular limitation as long as it functions as an infrared sensor.

Hereinafter, an embodiment of the infrared sensor of the present invention will be described with reference to FIG. 1.

In the infrared sensor 100 shown in FIG. 1, reference numeral 110 denotes a solid-state image sensor.

The imaging region provided on the solid-state imaging device 110 includes an infrared absorption filter 111 and a color filter 112.

The infrared absorption filter 111 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm), and transmits light in the infrared region (for example, light with a wavelength of 800 to 1300 nm, preferably with a wavelength of 900 to 1200 nm). It consists of shielding the light of, more preferably, light having a wavelength of 900 to 1000 nm).

The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible region are formed. For example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used.

A region 114 in which the infrared absorption filter 111 is not formed is provided between the infrared transmission filter 113 and the solid-state image sensor 110. In the region 114, a resin layer (for example, a transparent resin layer) capable of transmitting light having a wavelength transmitted through the infrared transmission filter 113 is disposed.

The infrared transmission filter 113 is a filter that has visible light shielding property and transmits infrared rays of a specific wavelength, and is constituted by the color filter (film) of the present invention having the above-described spectral characteristics. It is preferable that the infrared transmission filter 113 shields light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm.

A microlens 115 is disposed on the incident light hν side of the color filter 112 and the infrared transmission filter 113. A planarization layer 116 is formed to cover the micro lens 115.

In the embodiment shown in FIG. 1, the resin layer is disposed in the region 114, but the infrared transmission filter 113 may be formed in the region 114. That is, the infrared transmission filter 113 may be formed on the solid-state imaging device 110.

In addition, in the embodiment shown in FIG. 1, the film thickness of the color filter 112 and the film thickness of the infrared transmission filter 113 are the same, but the film thicknesses of both may be different.

Moreover, in the embodiment shown in FIG. 1, although the color filter 112 is provided on the incident light (hν) side than the infrared absorption filter 111, the order of the infrared absorption filter 111 and the color filter 112 is changed, and infrared rays The absorption filter 111 may be provided on the incident light (hν) side rather than the color filter 112.

In addition, in the embodiment shown in FIG. 1, the infrared absorption filter 111 and the color filter 112 are adjacently stacked, but both filters do not necessarily have to be adjacent, and another layer may be provided between them.

According to this infrared sensor, since image information can be read in real time, motion sensing or the like in which an object to detect motion can be recognized is possible. Furthermore, since distance information can be acquired, it is also possible to capture an image including 3D information.

Next, an imaging device will be described as an example to which the infrared sensor of the present invention is applied. Examples of the imaging device include a camera module.

2 is a functional block diagram of an imaging device. The imaging device includes a lens optical system 1, a solid-state imaging element 10, a signal processing unit 20, a signal switching unit 30, a control unit 40, a signal storage unit 50, and a light emission control unit. 60, an infrared light-emitting diode (LED) 70 of a light-emitting element emitting infrared light, and image output units 80 and 81 are provided. Further, as the solid-state imaging device 10, the infrared sensor 100 described above can be used. Further, all or part of the configurations other than the solid-state imaging device 10 and the lens optical system 1 may be formed on the same semiconductor substrate. For each configuration of the imaging device, reference can be made to the description of paragraphs 0032 to 0036 of JP2011-233983A, and this content is intended to be incorporated in the present specification.

<Image display device>

The filter produced by using the colored composition of the present invention can also be used for an image display device such as a liquid crystal display device or an organic electroluminescence (organic EL) display device. For example, by using together with each color pixel (for example, red, green, blue), it is possible to use it for the purpose of forming an infrared pixel in addition to each color display pixel.

For the definition of the display device and the details of each display device, for example, "Electronic Display Device (Akio Sasaki, published in 1990 Chosakai High School)", "Display Device (Sumiaki Ibuki, Tosho Sankyo Corporation)" ) Published in the first year of Heisei)", etc. In addition, about a liquid crystal display device, it describes in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published in 1994, Chosakai Kogyo)", for example. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in "Next-generation liquid crystal display technology".

The image display device may have a white organic EL element as a display element. As a white organic EL element, it is preferable to have a tandem structure. Regarding the tandem structure of an organic EL element, Japanese Patent Laid-Open Publication No. 2003-45676, supervised by Akiyoshi Mikami, "The forefront of organic EL technology development-high brightness, high precision, long lifespan, and a collection of know-how -", Joho Kyokai Kijutsu, 326 -It is stated on page 328, 2008. The spectrum of white light emitted by the organic EL device preferably has strong maximum emission peaks in the blue region (430 nm-485 nm), green region (530 nm-580 nm), and yellow region (580 nm-620 nm). In addition to these emission peaks, it is more preferable to further have a maximum emission peak in the red region (650 nm-700 nm).

Example

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it goes beyond the gist. In addition, unless otherwise specified, "parts" and "%" are based on mass.

(Test Example 1)

[Preparation of pigment dispersion 1-1 to 1-9]

The mixed liquid of the composition shown in the following table was mixed and dispersed in a bead mill (high pressure disperser NANO-3000-10 equipped with a pressure reducing device (manufactured by Nippon BEI Co., Ltd.)) using zirconia beads having a diameter of 0.3 mm. A dispersion was prepared. Moreover, about the pigment dispersion liquids 1-1 to 1-3 and 1-6 to 1-9, until the infrared absorber became the average particle diameter shown in the following table, it mixed and dispersed, and the pigment dispersion liquid was prepared. In the following table, the amount (unit: parts by mass) of the corresponding component is shown.

The average particle diameter of the pigment in the pigment dispersion was measured on a volume basis using MICROTRAC UPA 150 manufactured by Nikkiso Corporation. The measurement results are shown in the table below.

[Preparation of pigment dispersions 2-1 to 2-12, 3-1, 3-2]

A mixture of the following composition was mixed and dispersed for 3 hours using a bead mill (high pressure disperser NANO-3000-10 equipped with a pressure reducing device (manufactured by Nippon BEI Co., Ltd.)) using 0.3 mm diameter zirconia beads, and a pigment dispersion liquid Prepared. In the following table, the amount (unit: parts by mass) of the corresponding component is shown.

[Table 13]

The abbreviations of each component in the table are as follows.

Pyrrolopyrrole pigment 1: The following structure (synthesized by the method described in Japanese Patent Laid-Open No. 2009-263614) (Infrared absorber having maximum absorption in the range of wavelength 800 to 900 nm)

[Formula 71]

Pyrrolopyrrole pigment 2: The following structure (synthesized by the method described in Japanese Patent Laid-Open No. 2009-263614) (Infrared absorber having maximum absorption in the range of wavelength 800 to 900 nm)

[Chemical Formula 72]

Cyanine pigment: the following structure (infrared absorber having an absorption maximum in the range of 800 to 900 nm wavelength)

[Chemical Formula 73]

Squaarylium pigment: the following structure (infrared absorber having the maximum absorption in the range of wavelength 800 to 900 nm)

[Chemical Formula 74]

Infrared absorber 1: IRA842 (naphthalocyanine compound, manufactured by Exiton)

Infrared absorber 2: FD-25 (manufactured by Yamada Chemical Corporation)

TiOPc: oxo titanylphthalocyanine

VONPc: Oxovanadilnaphthalocyanine

[Coloring material that blocks light in the visible area]

PR 254: Pigment Red 254

PR 224: Pigment Red 224

PB 15:6: Pigment Blue 15:6

PY 139: Pigment Yellow 139

PY 185: Pigment Yellow 185

PV 23: Pigment Violet 23

PG 36: Pigment Green 36

PG 7: Pigment Green 7

PO 71: Pigment Orange 71

Black material 1: Irgaphor Black (manufactured by BASF)

Black material 2: Pigment Black 31

Black material 3: Pigment Black 32

[etc]

Carbon Black: Pigment Black 7

・Titanium Black: manufactured by Mitsubishi Material

[Suzy]

Dispersion resin 1: Disperbyk-111 (manufactured by BYK Chemie)

Dispersion resin 2: the following structure (Mw: 7950)

[Chemical Formula 75]

Dispersion resin 3: the following structure (Mw: 30000)

[Formula 76]

Dispersion resin 4: the following structure (Mw: 24000)

[Chemical Formula 77]

Dispersion resin 5: the following structure (Mw: 38900)

[Chemical Formula 78]

Alkali-soluble resin 1: the following structure (Mw: 12000)

[Chemical Formula 79]

[Organic solvents]

PGMEA: Propylene glycol methyl ether acetate

[Preparation of colored composition]

The components in the following table were mixed in the proportions described in the following table to prepare a colored composition. In the following table, the amount (unit: parts by mass) of the corresponding component is shown.

[Table 14]

[Table 15]

The abbreviations of each component in the table are as follows.

Pyrrolopyrrole dye 1: The following structure (synthesized by the method described in Japanese Patent Laid-Open No. 2009-263614) (Infrared absorber having maximum absorption in the range of wavelength 800 to 900 nm)

[Chemical Formula 80]

Pyrrolopyrrole dye 2: The following structure (synthesized by the method described in Japanese Patent Application Laid-Open No. 2009-263614) (Infrared absorber having maximum absorption in the range of wavelength 800 to 900 nm)

[Formula 81]

Polymerizable compound 1: M-305 (triacrylate 55-63 mass%, Toa Kosei Co., Ltd. product), mixture of the following compounds

[Formula 82]

Polymerizable compound 2: Dipentaerythritol hexaacrylate (A-DPH manufactured by Shinnakamura Chemical Industry Co., Ltd.)

Photoinitiator 1: IRGACURE OXE-01 (BASF) the following structure

[Formula 83]

Photoinitiator 2: IRGACURE OXE-02 (manufactured by BASF)

Adhesion improving agent 1: the following structure

[Formula 84]

Surfactant 1: Megapak F-781F (fluorinated polymer type surfactant, manufactured by DIC)

・Polymerization inhibitor 1: Paramethoxyphenol

Organic solvent 1: Propylene glycol methyl ether acetate

Organic solvent 2: Cyclohexanone

[Absorbance and spectral characteristics]

The colored composition was spin-coated on a glass substrate, and the film thickness after post-baking was 3.0 μm (Examples 1 to 27, Comparative Examples 1 to 3), or 1.5 μm (Example 28), and then 100° C., 120 After drying on a hot plate for a second and drying, heat treatment (post-baking) was further performed for 300 seconds using a hot plate at 200°C.

Using an ultraviolet visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High Technologies), the substrate having the colored layer has a light transmittance in the range of 300 to 1300 nm, and the minimum value A of the absorbance in the range of 400 to 830 nm. , The maximum value B of the absorbance in the range of wavelength 1000-1300 nm was measured.

[Production of color filter]

Each colored composition was coated on a silicon wafer using a spin coater so that the dried film thickness was 3.0 μm (Examples 1 to 27, Comparative Examples 1 to 3), or 1.5 μm (Example 28), and Heat treatment (pre-baking) was performed for 120 seconds using a hot plate of.

Then, the i-line stepper exposure apparatus FPA-3000i5 + (Canon (Ltd.)), an exposure amount by 50mJ / cm ² to 50 ~ 750mJ / cm ^2, using a photomask which is a square pixel pattern of square 1.4μm formed using It was raised to determine an optimal exposure amount for resolving the square pixel pattern, and exposure was performed at this optimal exposure amount.

After that, the silicon wafer on which the exposed coating film was formed is placed on a horizontal rotating table of a spin shower developer (DW-30 type, manufactured by Chemtronics Co., Ltd.), and CD-2060 (tetramethylammonium hydroxide aqueous solution) , Using a Fujifilm Electronic Materials Co., Ltd. product, puddle development was performed at 23°C for 60 seconds to form a colored pattern on a silicon wafer.

The silicon wafer on which the colored pattern was formed was rinsed with pure water, and then spray dried.

Further, heat treatment (post-baking) was performed for 300 seconds using a 200°C hot plate to obtain a silicon wafer having a colored pattern as a color filter.

<Evaluation>

[Heat resistance]

The color filter was heated on a hot plate at 260°C for 300 seconds. The transmittance (unit %) of light with respect to a wavelength of 400 to 830 nm of the color filter before and after heating was measured, and the change in transmittance was evaluated.

Transmittance change =|(Transmittance after heating (%)-Transmittance before heating (%))|

<Evaluation criteria>

3: The change in transmittance before and after heating is less than 3%

2: The change in transmittance before and after heating is 3% or more and less than 5%

1: Change of transmittance before and after heating is 5% or more

[Spectral recognition]

The obtained color filter was introduced into a solid-state imaging device according to a known method. In the obtained solid-state imaging device, a near-infrared LED light source having an emission wavelength of 940 nm was irradiated under a low-illuminance environment (0.001 Lux), and an image was read, and image performance was compared and evaluated. The evaluation criteria are shown below.

<Evaluation criteria>

3: Good, the subject can be clearly recognized on the image.

2: Slightly good, the subject can be recognized on the image.

1: Insufficient, the subject cannot be recognized on the image.

[Table 16]

All of the examples using the colored composition of the present invention transmitted infrared rays having an emission wavelength of 940 nm in a state where there was little noise derived from visible light, and the spectral recognition was good. On the other hand, in Comparative Examples 1 to 3, there were many noises derived from visible light, and the spectral recognition was insufficient.

(Test Example 2)

[Preparation of pigment dispersion 4-1 to 4-9]

The mixed solution of the composition shown in the following table was used as zirconia beads having a diameter of 0.3 mm, using a bead mill (high pressure disperser NANO-3000-10 equipped with a pressure reducing device (manufactured by Nippon BI Co., Ltd.)), and an infrared absorber was shown in the table below. Mixing and dispersing was performed until the average particle diameter described was reached, and a pigment dispersion was prepared. In the following table, the amount (unit: parts by mass) of the corresponding component is shown.

The average particle diameter of the pigment in the pigment dispersion was measured on a volume basis using MICROTRAC UPA 150 manufactured by Nikkiso Corporation. The results are shown in the table below.

[Table 17]

The abbreviations of each component in the table are as follows.

Pyrrolopyrrole pigment 1: Pyrrolopyrrole pigment 1 used in Test Example 1

TiOPc: oxo titanylphthalocyanine

VONPc: Oxovanadilnaphthalocyanine

PR 254: Pigment Red 254

PB 15:6: Pigment Blue 15:6

PGMEA: Propylene glycol methyl ether acetate

Dispersion resin 10: the following structure (Mw: 8500)

[Formula 85]

Dispersion resin 11: the following structure (Mw: 9200)

[Formula 86]

Dispersion resin 12: the following structure (Mw: 20000)

[Chemical Formula 87]

Pigment derivative 1: the following structure

[Formula 88]

[Preparation of colored composition]

The components in the following table were mixed in the proportions described in the following table to obtain a colored composition. The following table shows the amount of the corresponding component (unit: parts by mass).

[Table 18]

The abbreviations of each component in the table are as follows.

Pigment dispersions 2-1 to 2-4, polymerizable compound 1, alkali-soluble resin 1, photopolymerization initiator 1, surfactant 1, polymerization inhibitor 1, substrate adhesive 1, organic solvent 1, components shown in Tables 13 and 14 Is the same as

Photopolymerization initiator 3: the following structure

[Chemical Formula 89]

[Absorbance and spectral characteristics]

The coloring composition was spin-coated on a glass substrate, applied so that the film thickness after post-baking became 3.0 μm, dried on a hot plate at 100°C for 120 seconds, and then heat treated for 300 seconds using a hot plate at 200°C (post-baking ) Did more.

Using an ultraviolet visible near-infrared spectrophotometer U-4100 (manufactured by Hitachi High Technologies) (ref. glass substrate), a substrate having a colored layer is applied to a light transmittance in the range of 300 to 1300 nm and a wavelength of 400 to 830 nm. The minimum value A of absorbance in and the maximum value B of absorbance in a range of 1000 to 1300 nm in wavelength were measured.

[Production of color filter]

Except that the coloring composition was coated on a silicon wafer with a spin coater so that the film thickness after drying became 3.0 μm, and heat treatment (prebaked) was performed for 120 seconds using a hot plate at 100°C, as in Test Example 1 A color filter was produced in the same way.

<Evaluation>

In the same manner as in Test Example 1, heat resistance and spectral recognition were evaluated.

[Table 19]

All of the examples using the colored composition of the present invention transmitted infrared rays having an emission wavelength of 940 nm in a state where there was little noise derived from visible light, and the spectral recognition was good.

<Test Example 3>

[Preparation of pigment dispersion 5-1]

9.2 parts by mass of oxo titanylphthalocyanine (TiOPc) pigment, 3.2 parts by mass of CI Pigment Blue 15:6, 25.6 parts by mass of dispersion resin, 82.0 parts by mass of PGMEA, using 0.3 mm diameter zirconia beads, a bead mill (decompression mechanism With the attached high-pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.), until the average particle diameter of the TiOPc pigment became 100 nm or less, it was mixed and dispersed to prepare a pigment dispersion liquid 5-1. The average particle diameter of the pigment in the pigment dispersion was measured on a volume basis using MICROTRAC UPA 150 manufactured by Nikkiso Corporation.

[Preparation of colored composition]

The components in the following table were mixed in the proportions described in the following table to prepare a colored composition. In the following table, the amount (unit: parts by mass) of the corresponding component is shown.

[Table 20]

The materials shown in the table are as follows.

Pigment Dispersion 5-1: The Pigment Dispersion

Pigment dispersions 2-1, 2-2, polymerizable compounds 1 and 2, alkali-soluble resin 1, photopolymerization initiator 3, substrate adhesive 1, surfactant 1, polymerization inhibitor 1, organic solvent 1: In Test Examples 1 and 2 Same as the material used

Polymerizable compound 3: Aronix M-315 (isocyanuric acid ethylene oxide modified die and triacrylate, diacrylate is 3 to 13% by mass, Toa Kosei Co., Ltd. product), a mixture of the following compounds

[Chemical Formula 90]

Polymerizable compound 4: A-TMMT (pentaerythritol tetraacrylate: Shinnakamura Chemical Co., Ltd. product)

Photopolymerization initiator 4: Adeka Arcles NCI-831 (made by ADEKA)

[Formula 91]

Photopolymerization initiator 5: the following structure

[Formula 92]

Photopolymerization initiator 6: IRGACURE-369 (manufactured by BASF)

Photoinitiator 7: IRGACURE-2959 (manufactured by BASF)

Photopolymerization initiator 8: IRGACURE-819 (manufactured by BASF)

Surfactant 2: KF6001 (manufactured by Shin-Etsu Silicone Co., Ltd.)

Epoxy compound 1: EPICLON N-695 (manufactured by DIC Corporation)

Epoxy compound 2: jER1031S (manufactured by Mitsubishi Chemical Corporation)

Epoxy compound 3: EHPE 3150 (manufactured by Daicel)

[Evaluation of absorbance and spectral characteristics]

Using the above colored composition. In the same manner as in Test Example 1, a cured film was produced so that the film thickness after post-baking became 2.0 μm, and the spectral properties of the obtained cured film were evaluated.

[Production of color filter and evaluation of heat resistance]

Using the colored composition, except having applied the colored composition so that the film thickness after drying becomes 2.0 μm, a color filter was prepared in the same manner as in Test Example 1, and heat resistance was evaluated in the same manner as in Test Example 1.

[Table 21]

All of the examples using the colored composition of the present invention transmitted infrared rays having an emission wavelength of 940 nm in a state where there was little noise derived from visible light, and the spectral recognition was good.

<Test Example 4>

[Preparation of pigment dispersion 6-1]

9.2 parts by mass of vanadium phthalocyanine (VOPc) pigment, 3.2 parts by mass of CI Pigment Blue 15:6, 25.6 parts by mass of dispersion resin, 82.0 parts by mass of PGMEA, using 0.3 mm diameter zirconia beads, a bead mill (with a pressure reducing device) With a high-pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.), it was mixed and dispersed until the average particle diameter of the TiOPc pigment became 100 nm or less, and a pigment dispersion liquid 6-1 was prepared. The average particle diameter of the pigment in the pigment dispersion was measured on a volume basis using MICROTRAC UPA 150 manufactured by Nikkiso Corporation.

[Preparation of pigment dispersion 6-2]

Using 13.5 parts by mass of the following cyanine compound I-13, 4 parts by mass of the dispersion resin 1 (Disperbyk-111 (manufactured by BYK Chemie)) and 82.5 parts by mass of PGMEA using 0.3 mm diameter zirconia beads, a bead mill (decompression mechanism It was mixed and dispersed with an attached high-pressure disperser NANO-3000-10 (manufactured by Nippon BEI Co., Ltd.) to prepare a pigment dispersion liquid 6-2.

[Preparation of pigment dispersion 6-3]

Using 13.5 parts by mass of the following cyanine compound I-14, 4 parts by mass of the dispersion resin 1 (Disperbyk-111 (manufactured by BYK Chemie)), and 82.5 parts by mass of PGMEA using 0.3 mm diameter zirconia beads, a bead mill (decompression mechanism It mixed and dispersed with the attached high-pressure disperser NANO-3000-10 (manufactured by Nippon BEI Co., Ltd.) to prepare a pigment dispersion liquid 6-3.

[Preparation of pigment dispersion 6-4]

Using 13.5 parts by mass of the following cyanine compound I-15, 4 parts by mass of the dispersion resin 1 (Disperbyk-111 (manufactured by BYK Chemie)), and 82.5 parts by mass of PGMEA using 0.3 mm diameter zirconia beads, a bead mill (decompression mechanism It mixed and dispersed with the attached high-pressure disperser NANO-3000-10 (manufactured by Nippon Biei Co., Ltd.) to prepare a pigment dispersion liquid 6-4.

Cyanine compounds I-13 to I-15: the following structures

[Chemical Formula 93]

[Preparation of colored composition]

The components in the following table were mixed in the proportions described in the following table to prepare a colored composition. In the following table, the amount (unit: parts by mass) of the corresponding component is shown.

[Table 22]

The materials shown in the table are as follows.

Pigment dispersion 5-1, 2-1 to 2-5, 2-9, polymerizable compounds 1 to 4, alkali-soluble resin 1, photopolymerization initiator 3 to 8, substrate adhesive 1, epoxy compound 1, surfactant 1, 2 , Polymerization inhibitor 1, organic solvent 1, 2: same as the material used in Test Examples 1 and 2

Pigment dispersion liquid 6-1 to 6-4: the pigment dispersion liquid

Cyanine compound I-13 to I-14: the compound

Polymerizable compound 5: Aronics M-313 (isocyanuric acid ethylene oxide modified die and triacrylate, manufactured by Toa Kosei Co., Ltd.)

Photopolymerization initiator 9: IRGACURE-379 (manufactured by BASF)

Alkali-soluble resin 2: Cyclomer P (ACA) 230AA (manufactured by Daicel)

[Evaluation of absorbance and spectral characteristics]

(Test Example 4-1-1)

Using the colored compositions of Examples 301 to 309, in the same manner as in Test Example 1, a cured film was produced so that the film thickness after post-baking became 2.0 μm, and the spectral properties of the obtained cured film were evaluated.

(Test Example 4-1-2)

Using the colored composition of Examples 310 to 312, a cured film was produced in the same manner as in Test Example 1 so that the film thickness after post-baking became 2.4 μm, and the spectral properties of the obtained cured film were evaluated.

[Production of color filter and evaluation of heat resistance]

(Test Example 4-2-1)

A color filter was prepared in the same manner as in Test Example 1, except that the colored composition was applied so that the film thickness after drying was 2.0 μm using the colored composition of Examples 301-309, and heat resistance was achieved in the same manner as in Test Example 1. Evaluated.

(Test Example 4-2-1)

A color filter was prepared in the same manner as in Test Example 1, except that the colored composition was applied so that the film thickness after drying was 2.4 μm using the colored composition of Examples 310 to 312, and heat resistance was obtained in the same manner as in Test Example 1. Evaluated.

[Table 23]

All of the examples using the colored composition of the present invention transmitted infrared rays having an emission wavelength of 940 nm in a state where there was little noise derived from visible light, and the spectral recognition was good.

1: lens optical system
10: solid-state imaging device
20: signal processing unit
30: signal switching unit
40: control unit
50: signal accumulation unit
60: light emission control unit
70: infrared LED
80, 81: image output unit
100: infrared sensor
110: solid-state image sensor
111: infrared absorption filter
112: color filter
113: infrared transmission filter
114: area
115: micro lens
116: planarization layer
hν: incident light

Claims (21)

As an infrared transmissive composition containing a colorant for blocking visible light and an infrared absorber,
The colorant for blocking visible light is a colorant for blocking light in a wavelength range of 450 to 650 nm, the infrared absorber is a compound having an absorption maximum in a wavelength range of 800 to 1300 nm, and a pyrrolopyrrole compound , At least one selected from a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound, an infrared transmissive composition. The method according to claim 1,
The infrared-transmitting composition, wherein the colorant for blocking light in the visible region contains two or more chromatic colorants, and forms black by a combination of two or more chromatic colorants. The method according to claim 1,
The infrared-transmitting composition, wherein the colorant for blocking light in the visible region contains an organic black colorant. The method of claim 3,
The organic black colorant is at least one selected from a perylene compound and a bisbenzofuranone compound, an infrared transmissive composition. The method of claim 4,
An infrared transmissive composition further comprising a chromatic colorant. The method according to claim 2 or 5,
The chromatic colorant is selected from a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. delete The method according to claim 1,
The pyrrolopyrrole compound is a pigment, infrared transmissive composition. The method according to claim 1,
The pyrrolopyrrole compound is an infrared transmissive composition represented by the following formula (1);
[Formula 1]

In formula (1), R ^1a and R ^1b each independently represent an alkyl group, an aryl group or a heteroaryl group, R ² and R ³ each independently represent a hydrogen atom or a substituent, and R ² and R ³ are, They may be bonded to each other to form a ring, and R ⁴ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR ^4A R ^4B , or a metal atom, and R ⁴ represents R ^1a , R ^1b and At least one selected from R ³ may be a covalent bond or a coordination bond, and R ^4A and R ^4B each independently represent a hydrogen atom or a substituent. The method according to any one of claims 1 to 5,
An infrared transmissive composition further comprising a polymerizable compound. The method of claim 10,
An infrared transmissive composition further comprising a photopolymerization initiator. The method according to any one of claims 1 to 5,
An infrared transmissive composition used for manufacturing a color filter. A film formed by curing the infrared-transmitting composition according to any one of claims 1 to 5. A color filter having the film according to claim 13. A process of forming a colored composition layer on a support by using the infrared transmissive composition according to any one of claims 1 to 5, a process of exposing the colored composition layer in a pattern shape, and developing and removing an unexposed part to a colored pattern A pattern forming method comprising a step of forming a. A method for manufacturing a color filter, including the pattern formation method according to claim 15. A solid-state imaging device comprising the color filter according to claim 14. An infrared sensor having the color filter according to claim 14. delete As a coloring composition containing a color material that blocks light in the visible region and an infrared absorber,
The colorant for blocking visible light is a colorant for blocking light in a wavelength range of 450 to 650 nm, the infrared absorber is a compound having an absorption maximum in a wavelength range of 800 to 1300 nm, and a pyrrolopyrrole compound , At least one selected from a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound,
The coloring composition which is selected from organic pigments or dyes, or organic black colorants, as the color material that blocks light in the visible region. As a coloring composition containing a color material that blocks light in the visible region and an infrared absorber,
The colorant for blocking visible light is a colorant for blocking light in a wavelength range of 450 to 650 nm, the infrared absorber is a compound having an absorption maximum in a wavelength range of 800 to 1300 nm, and a pyrrolopyrrole compound , At least one selected from a phthalocyanine compound, a naphthalocyanine compound, and a polymethine compound,
A colored composition containing 10 to 200 parts by mass of the infrared absorber with respect to 100 parts by mass of a color material that blocks light in the visible region.

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